Ink for inkjet recording

ABSTRACT

An ink for inkjet recording includes water; a hydrosoluble solvent, a pigment, and a copolymer including a salt of a diphosphonic acid group. The copolymer including a salt of a diphosphonic acid group includes structural units having the following formulae (1) and (2): 
     
       
         
         
             
             
         
       
     
     X represents an alkylene group having 1 to 3 carbon atoms, each of R 1  and R 2  represents a hydrogen atom or a methyl group, M +  represents an alkali metal ion, an organic ammonium ion or a proton and Z 1  represents a hydrocarbon group having 6 to 22 carbon atoms. The alkali metal ion or the organic ammonium ion and the proton may be mixed, and half or more of the M +  are alkali metal ions or the organic ammonium ions.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application is based on and claims priority pursuant to 35U.S.C. §119 to Japanese Patent Application No. 2013-174231, 2014-089099and 2014-086159, filed on Aug. 26, 2013, Apr. 23, 2014 and Apr. 18, 2014in the Japan Patent Office, the entire disclosure of which is herebyincorporated by reference herein.

BACKGROUND

1. Technical Field

The present invention relates to an ink for inkjet recording(hereinafter referred to as an “ink”), an ink cartridge, and an inkjetrecorder.

2. Description of the Related Art

Inkjet recording methods have been popular as image forming methodsbecause of having advantages of having simpler process and easierfull-colorization than the other recording methods, and producinghigh-resolution images even with an apparatus having simple composition.The inkjet recording methods have a small amount of ink soar and adhereto recording media such as papers to form images thereon with an inkjetrecorder, and applications thereof are expanding, e.g., personal andindustrial printers and printings.

In the inkjet recording methods, an aqueous ink using a water-solubledye is mostly used as a colorant. However, the ink has disadvantages ofhaving poor weatherability and water resistance. Therefore, a pigmentink using a pigment instead of the water-soluble dye has been studiedrecently. However, the pigment ink is still inferior to the dye ink incolorability, ink discharge stability and preservation stability.

In company with improvement of higher-quality image technology of OAprinters, even when recorded on plain papers as recording media with thepigment ink, image density equivalent to that of the dye ink isrequired. However, the pigment ink penetrates into a plain paper as arecording medium and pigment density at the surface of the paper lowers,resulting in lower image density.

In order to dry the ink adhering to the recording medium quicker toprint quicker, a penetrant is added to the ink for water to penetrateinto the recording medium. Then, not only water but also pigmentpenetrates deeper into the recording medium, resulting in lower imagedensity.

When a plain paper is used as a recording medium, the surface of theplain paper swells due to water which is a solvent of the ink and adifference of extension rate between the front side and the back side ofthe paper becomes large, resulting in curl. This has not been a problemin low-speed printing because of being solved as the paper is dried.

However, in high-speed printing, paper jam may occur because a recordingmedium is fed with curl unsolved. An organic solvent in the ink iseffectively increased to solve curl. However, it becomes difficult toassure storage stability of the ink because of being more hydrophobic.

In order to solve this problem, PCT Japanese published national phaseapplication No. 2009-513802 discloses an inkjet composition including aliquid vehicle, a colorant, and a polymer having at least one functionalgroup having a specific calcium index value. Monomers forming thepolymer include 4-methacrylamide-1-hydroxybutane-1,1-diphosphonic acid.The colorant is destabilized by the diphosphonic acid group and Ca saltin a paper when contacting the paper, and the resultant printed imageimproves in quality.

Japanese published unexamined application No. JP-2012-51357-A disclosesan inkjet recording method of applying a receiving liquid including a Casalt; and an ink including a pigment combined with a group havingphosphorus, a resin emulsion and a surfactant thereon. It is disclosedthat a bisphosphonic acid is preferably used as the group havingphosphorus, which is reacted with the Ca salt in the receiving liquid toimprove feathering and fixability. However, a polymer includingphosphonic acid group is not used as dispersant or an additive in apigment dispersion, and a pigment combined with a phosphoric acid isused. Therefore, image density of an image recorded on a plain paper isnot sufficiently improved. Further, the surface of a pigment needschemical decoration, and the selection thereof is limited.

Japanese published unexamined application No. JP-2004-123904-A disclosesan aqueous ink including a colorant, water, hydrosoluble organicsolvent, a surfactant and a chelate agent. A low-molecular-weighthydroxy ethylidenediphosphonic acid or its salt is used as the chelateagent. The chelate agent removes calcium included in a pigmentdispersion to improve discharge stability and storage stability of theink. However, only the low-molecular-weighthydroxyethylidenediphosphonic acid is disclosed, and a polymer includinga phosphonic acid is not disclosed. A relation between the chelate agentand improvement of the image density of an image when recorded on aplain paper is not disclosed, either.

SUMMARY

Accordingly, a need exist for an ink for inkjet recording, forming animage having high image density even on a plain paper, good storagestability even when including a hydrosoluble organic solvent in a largeamount, and using a general-use pigment.

Another object of the present invention is to provide an ink cartridgecontaining the ink.

A further object of the present invention is to provide an inkjetrecording method using the ink.

Another object of the present invention is to provide an inkjet recorderusing the ink.

A further object of the present invention is to provide a recordedmatter recorded by the ink.

These objects and other objects of the present invention, eitherindividually or collectively, have been satisfied by the discovery of anink for inkjet recording, including water, a hydrosoluble solvent, apigment, and a copolymer including a salt of a diphosphonic acid group;wherein the copolymer including a salt of a diphosphonic acid groupincludes structural units having the following formulae (1) and (2):

wherein X represents an alkylene group having 1 to 3 carbon atoms, eachof R₁ and R₂ represents a hydrogen atom or a methyl group, M⁺ representsan alkali metal ion, an organic ammonium ion or a proton and Z₁represents a hydrocarbon group having 6 to 22 carbon atoms, wherein thealkali metal ion or the organic ammonium ion and the proton may bemixed, and half or more of the M⁺ are alkali metal ions or the organicammonium ions.

The copolymer including a salt of a diphosphonic acid group may furtherinclude a structural unit having the following formula (3a) or (3b):

wherein R₃ represents a hydrogen atom or a methyl group; each of R₁₀ andR₁₁ represents an alkyl group having 1 to 3 carbon atoms; Y representsan alkylene group having 1 to 4 carbon atoms; and Y₁ represents analkylene group having 1 to 3 carbon atoms.

These and other objects, features and advantages of the presentinvention will become apparent upon consideration of the followingdescription of the preferred embodiments of the present invention takenin conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

Various other objects, features and attendant advantages of the presentinvention will be more fully appreciated as the same becomes betterunderstood from the detailed description when considered in connectionwith the accompanying drawings in which like reference charactersdesignate like corresponding parts throughout and wherein:

FIG. 1 is a schematic plain view illustrating an embodiment of the inkcontainer of the present invention;

FIG. 2 is a schematic plain view illustrating the ink container of thepresent invention including a case (outer package) in FIG. 1;

FIG. 3 is a perspective view illustrating an embodiment of the inkjetrecorder of the present invention;

FIG. 4 is a schematic view illustrating an overall structure of theinkjet recorder in FIG. 3; and

FIG. 5 is an enlarged partial view of the inkjet recorder in FIG. 3.

DETAILED DESCRIPTION

The present invention provides an ink for inkjet recording, forming animage having high image density even when using a pigment withoutchemical decoration including a phosphorous-containing group on a plainpaper and having good storage stability even when including ahydrosoluble organic solvent in a large amount.

Specific examples of the alkali metal in the alkali metal ion of M⁺ inthe formula (1) include, but are not limited to, lithium, sodium andpotassium.

Specific examples of the organic amine in the organic ammonium ion of M⁺include, but are not limited to, alkyl amines such as mono, di ortrimethylamine and mono, di or triethylamine; alcohol amines such asethanol amine, diethanolamine, triethanolamine,methylethanolamine(2-(methylamine)ethanol), methyldiethanolamine,dimethylethanolamine, monopropanolamine, dipropanolamine,tripropanolamine, isopropanolamine, trishydroxymethylaminomethane and2-amino-2-ethyl-1,3propanedil (AEPD); and cyclic amine such as choline,morpholine, N-methylmorpholine, N-methyl-2-pyrrolidone and2-pyrrolidone.

Quaternary organic ammonium ions are preferably used as the organicammonium ions of M⁺ as well. Specific examples thereof include, but arenot limited to, tetramethylammonium ions, tetraethylammonium ions,tetrapropylammonium ions, tetrabutylammonium ions, tetraamylammoniumions, benzyltrimethylammonium ions, hydroxyethyltrimethylammonium ions,methyltrioctylammonium ions and trimethylstearylammonium ions.

Particularly, the potassium ion, sodium ion and alkyl ammonium ion arepreferably used.

In the alkyl ammonium ions, tetraalkylammonium ions having 1 to 5 alkylgroups are more preferably used because of being capable of providing anink having low viscosity and good storage stability.

Specific examples thereof include, but are not limited to,tetraethylammonium ions, tetrabutylammonium ions, methyltributylammoniumions, methyltriamylammonium ions, triethylmethylammonium ions andethyltrimethylammonium ions.

Not less than half or all of M⁺ are preferably alkali metal ions ororganic ammonium ions, and the rest is preferably a hydrogen ion(proton).

Specific examples of the alkylene group having 1 to 3 carbon atoms of Xin the formula (1) include q methylene group, an ethylene group and apropylene group.

Specific examples of the hydrocarbon group having 6 to 22 carbon atomsused as Z₁ in the formula (2) include, but are not limited to, aromatichydrocarbon groups such as a phenyl group and a naphthyl group; cyclicsaturated hydrocarbon groups such as a cyclohexyl group; chain saturatedhydrocarbon groups such as a dodecyl group, a stearyl group and anisostearyl group; aralkyl groups such as a benzyl group; and chainunsaturated hydrocarbon groups such as a 9-octadecenyl group.

Particularly, the benzyl group, a phenetyl group and an alkyl grouphaving 12 to 22 carbon atoms are preferably used. Specific examples ofthe alkyl group having 12 to 22 carbon atoms include, but are notlimited to, straight-chain or branched-chain alkyl groups such as adodecyl group, a tetradecanyl group, a hexadecanyl group, an octadecanylgroup and a docosanyl group.

The structural unit having the formula (1) preferably has a weight ratioof from 30 to 70% by weight, more preferably from 40 to 60% by weight,and furthermore preferably from 45 to 55% by weight in terms of highimage density, and good dispersion and storage stability of theresultant ink.

The copolymer including a salt of a phosphonic acid group used in thepresent invention can be prepared by the following method of preparingthe polymer of the present invention. The copolymer including thestructural units having the formulae (1) and (2) can widely be used invarious fields, and is preferably used as a pigment dispersant, apigment concentration improver, a binder resin for pigment and aviscosity adjustor in an ink for inkjet recording

<Method of Preparing Polymer>

The polymer for use in the present invention can be synthesized byradically polymerizing polymeric materials including compounds(monomers) having the following formulae (4) and (5) to prepare apolymer, and neutralizing the polymer with an alkali metal base, anorganic amine base or an organic ammonium base:

wherein X represents an alkylene group having 1 to 3 carbon atoms, eachof R₄ and R₅ represents a hydrogen atom or a methyl group, M⁺ representsan alkali metal ion, an organic ammonium ion or a proton and Z₂represents a hydrocarbon group having 6 to 22 carbon atoms.

The polymeric materials may further include a monomer having thefollowing formula (6a) or (6b):

wherein R₆ represents a hydrogen atom or a methyl group; each of R₁₂ andR₁₃ represents an alkyl group having 1 to 3 carbon atoms; Y representsan alkylene group having 1 to 4 carbon atoms.

The number of acid groups of from 0 to 4 out of 4 in the formula (1) tobe neutralized can be adjusted. The number of the acid groups to beneutralized in the formula (1), i.e. the number of M⁺ is preferably from2 to 4, and more preferably 3.

Specific examples of the monomer having the formula (4) include, but arenot limited to, sodiumhydrogen-1-hydroxy-4-methacrylamide-1-phosphonobutylphosphonate, sodium1-hydroxy-4-methacrylamidebutane-1,1-diylbis(hydrogenphosphonate),sodium1-(hydrogenphosphonate)-1-hydroxy-4-methacrylamidebutylphosphonate andsodium 1-hydroxy-4-methacrylamidebutane-1,1-diyldiphosphonate.

These methacryl may be acryl, and sodium may be potassium or an organicammonium ion.

Even when M⁺ are all proton, these can be used as a monomer of1-hydroxy-4-methacrylamidebutane-1,1-diyldiphosphonate.

A monomer having the formula (4), e.g.,1-hydroxy-4-(meth)acrylamidebutane-1,1-diyldiphosphonic acid when X ispropylene can be prepared by neutralizing an alendronic acid with analkali metal base, an organic amine base or an organic ammonium base ina range of from 1 to 3 equivalents, and reacting the neutralizedalendronic acid with (meth)acrylic acid chloride.

The number of salts can be adjusted after the reaction.

Specific examples of the hydrocarbon group having 6 to 22 carbon atomsused as Z₂ in the formula (5) include, but are not limited to, aromatichydrocarbon groups such as a phenyl group and a naphthyl group; cyclicsaturated hydrocarbon groups such as a cyclohexyl group; chain saturatedhydrocarbon groups such as a dodecyl group, a stearyl group and anisostearyl group; aralkyl groups such as a benzyl group; and chainunsaturated hydrocarbon groups such as a 9-octadecenyl group.

Specific examples of monomers of the aromatic hydrocarbon groups such asa phenyl group and a naphthyl group of the hydrocarbon group having 6 to22 carbon atoms include, but are not limited to, phenyl(meth)acrylateand naphthyl(meth)acrylate. Specific examples of monomers of the cyclicsaturated hydrocarbon groups such as a cyclohexyl group of thehydrocarbon group having 6 to 22 carbon atoms include, but are notlimited to, cyclohexyl(meth)acrylate.

Specific examples of monomers of the chain saturated hydrocarbon groupssuch as a dodecyl group, a stearyl group and an isostearyl group of thehydrocarbon group having 6 to 22 carbon atoms include, but are notlimited to, hexyl(meth)acrylate, 2-ethyl hexyl(meth)acrylate,octyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate,dodecyl(meth)acrylate, hexadecyl(meth)acrylate, oxadecyl(meth)acrylateand dococyl(meth)acrylate.

Specific examples of monomers of the aralkyl groups such as a benzylgroup of the hydrocarbon group having 6 to 22 carbon atoms include, butare not limited to, benzyl(meth)acrylate and phenetyl(meth)acrylate.

Specific examples of monomers of the chain unsaturated hydrocarbongroups such as a 9-octadecenyl group of the hydrocarbon group having 6to 22 carbon atoms include, but are not limited to, oleyl(meth)acrylate.

(Meth)acrylate represents both of methacrylate and acrylate.

Specific examples of the monomer having the formula (5) include, but arenot limited to, benzylacrylate, benzyl methacrylate, phenetyl acrylate,phenetyl methacrylate, cyclohexylacrylate, cyclohexylmethacrylate,dodecylacrylate, dodecylmethacrylate, hexadecanyl acrylate, hexadecanylmethacrylate, octadecanyl acrylate, octadecanyl methacrylate, icosanylacrylate, icosanyl methacrylate, docosanyl acrylate and docosanylmethacrylate.

Specific examples of monomers having the formula (6a) include, but arenot limited to, 3-dimethylaminopropylacrylamide,3-diethylaminopropylacrylamode, 3-fi-n-propylaminopropylacrylamide,3-di-isopropylaminoprppylacrylamide, 3-ethylmethylaminopropylacrylamide,3-ethylisopropylaminopropylacrylamide, 2-dimethylaminoethylacrylamide,2-diethylaminoethylacrylamide, 2-disopropylaminoethylacrylamide,2-ethylmethylaminopropylacrylamide, dimethylamino methyl acrylamide anddiethylamino methyl acrylamide,

Specific examples of monomers having the formula (6b) include, but arenot limited to, trimethyl(meth)acryloyloxy methylammonium chloride,trimethyl-2-(meth)acryloyloxy methylammonium chloride andtrimethyl-3-(meth)acryloyloxy propyl ammonium chloride.

The monomers having the formulae (6a) and (6b) may be combined.

The polymer including the structural units having the formulae (1), (2),(3a) and (3b) is synthesized by known methods such as bulkpolymerization methods, solution polymerization methods, suspensionpolymerization methods and emulsion polymerization methods. A radicalpolymerization initiator is preferably used because polymerizingoperation and molecular weight control are easy. A solutionpolymerization method of polymerizing in a mixed solution of an organicsolvent and water is more preferably used.

A solvent used for radical polymerization by the solution polymerizationmethod is not particularly limited. The monomer having the formula (5)and optionally the monomer having the formula (6a) or (6b) dissolved inan organic solvent is preferably fed to an aqueous solution of themonomer having the formula (4) to be polymerized. Therefore, the organicsolvent is preferably hydrosoluble. Specific examples thereof include,but are not limited to, alcohol solvents such as methanol and ethanol;ether solvents such as tetrahydrofuran; and amide solvents such asN,N-dimethylformamide.

Specific examples of radical polymerization initiators include, but arenot limited to, such as peroxyketal, hydroperoxide, dialkylperoxide,diacylperoxide, peroxydicarbonate, peroxyester, cyanoazobisisobutylonitrile, azobis(2,2′-isovaleronitrile), and non-cyanodimethyl-2,2′-azobisisobutylate. Organic peroxides and azo compoundshaving an easily-controllable molecular weight and a low decompositiontemperature are preferably used, and the azo compounds are morepreferably used. The polymerization initiators are preferably used in anamount of from 1 to 20% by weight based on total weight of polymerizablemonomers.

In order to control a molecular weight of the polymer, chain transferagents such as mercaptoacetate, mercaptopropionate, 2-propanethiol,thiophenol, dodecylmercaptane, 1-dodecanethiol and α-thioglycerol may beadded in a proper amount.

Typically, the polymerization temperature is preferably from 50 to 150°C., and more preferably from 60 to 100° C.

The polymerization time is preferably from 3 to 48 hrs.

The polymer is neutralized with an alkali metal base or an organic aminebase.

The alkali metal base or the organic amine base can neutralize a part orall of phosphonic acid groups of the polymer.

When the neutralization is completed in the process of preparing themonomer having the formula (4), this neutralization process can beomitted. Typically, 1 to 2 equivalents are neutralized in the process ofpreparing the monomer and the rest acidic groups are neutralized afterpolymerized.

The neutralization with the alkali metal base or the organic amine basecan be made while a pigment and the polymer are mixed in the process ofpreparing an ink.

Specifically, in a flask equipped with a stirrer, a thermometer, aninactive gas (nitrogen or argon) inlet tube and a condenser, materialssuch as an aqueous solution including the monomer having the formula(4), an organic solvent solution including the monomer having theformula (5), optionally the monomer having the formula (6a) or (6b), apolymerization initiator and a molecular weight regulator are placed andstirred in a batch or continuously under an inactive gas. After reactedat from 60 to 150° C., the solution is neutralized with the alkali metalbase or the organic amine base.

The neutralization can be controlled according to an acid value of theresin.

The acid value of a resin is measured by dissolving or dispersing aweighed resin in water, a hydrosoluble organic solvent or their mixedsolvent and subjecting the solution or the dispersion to neutralizationtitration with a potassium hydroxide methanol solution having a specificconcentration and a thymolphthalein as an indicator.

In the present invention, 3 out of 4 acid groups of the bisphosphonicacid compound are neutralized when the thymolphthalein changes in color(pH of from 8 to 9). Therefore, when the acid value is measured with athymolphthalein as an indicator and a base is placed according thereto,a structure in which 3 acid groups are neutralized is formed.

When synthesized, the monomer having the formula (5) is preferablyincluded in an amount of from 30 to 70% by weight, more preferably from40 to 60% by weight, and furthermore preferably from 45 to 55% by weightper 100% by weight of the monomer having the formula (4).

The resultant polymer (copolymer) has a molecular weight distributionaccording to a polymerization degree. Typically, the molecular weight ismeasured by gel permeation chromatography (GPC) with ease. However, thepolymer is a dissociative polymer and difficult to measure due toadsorption to GPC column.

In the present invention, a viscosity of the polymer when being asolution having a specific concentration is a substitutional propertyinstead of the molecular weight. The viscosity is measured as follows.An aqueous solution including the copolymer in an amount of 10% byweight is prepared. According to the viscosity of a sample, theviscosity is measured by viscometer RE500L from TOKI SANGYO CO., LTD. at50 or 100 rpm.

An aqueous solution (10% by weight at 25° C.) of the copolymer includinga salt of the phosphonic acid group of the present invention preferablyhas a viscosity of from 1.5 to 4.0 mPa·s, and more preferably from 1.7to 3.0 mPa·s.

When not less than 1.5 mPa·s, the molecular weight is suitable anddispersion stability is good, and deterioration of image density isdifficult to occur due to lowering of calcium reactability. When notgreater than 4.0 mPa·s, the molecular weight is not too excessive, whichprevents the ink from increasing in viscosity, and the inkjet head fromclogging and defectively discharging. In addition, deterioration ofstorageability of a pigment dispersion and an ink are difficult to occurdue to deterioration of dispersibility and dispersion stability.

When from 1.7 to 3.0 mPa·s, deterioration of image density and inkstorageability are more difficult to occur. Deterioration of inkstorageability causes clogged head and defective discharge.

The molecular weight of the polymer including the structural units (1)and (2), and optionally (3a) or (3b) can be controlled rather by thepolymerization temperature, an amount of the polymerization initiatorand concentrations of the monomers when reacted.

The resultant polymer tends to have a low molecular weight whenpolymerized at high temperature for a short time, and a high molecularweight when polymerized at low temperature for a long time.

The resultant polymer tends to have a low molecular weight when thecontent of the polymerization initiator is high, and a high molecularweight when the content of the polymerization initiator is low.

The resultant polymer tends to have a low molecular weight when theconcentrations of the monomers are high, and a high molecular weightwhen concentrations of the monomers are low.

The content of the chain transfer agent can control the molecular weightof the copolymer of the present invention. The chain transfer agent isknown to receive a radical from a grown polymer chain to stop thepolymer from elongating. The chain transfer agent having received aradical attacks a monomer to resume polymerization, which contributes tocontrol of a molecular weight distribution and an average molecularweight.

(Ink for Inkjet Recording)

The ink for inkjet recording of the present invention includes water, ahydrosoluble solvent, a pigment, and a copolymer including a salt of adiphosphonic acid group including structural units having the formulae(1) and (2), and optionally (3a) or (3b).

<Copolymer Including Structural Units Having Formulae (1) and (2), andOptionally (3a) or (3b)>

The polymer including the structural unit having the formula (1) in theink for inkjet recording of the present invention has a dibasic acidstructure of adjacent phosphonic acids. In contrast to alow-molecular-weight compound, the polymer includes many diphosphonicacid groups in its molecule. As a result, the polymer including thestructural unit having the formulae (1) has better hydrophilicity than amonobasic acid because of being capable of including more hydrophilicgroups. In addition, the polymer includes a phosphonic acid groupreadily reactable with Ca ions, and has an effect of chelating Ca ionsbecause of being a dibasic acid. When contacting Ca ions, the polymermore firmly combines therewith to be hydrophobized.

The structural unit having the formula (2) brings hydrophobicity to thepolymer, increases wettability and adsorptivity with a pigment toimprove dispersion stability. Further, the polymer improvesaggregability of a resin when contacting Ca ions because of a balancewith the hydrophilic phosphonic acid group having the formula (1). Inaddition, the reason is not known, but the polymer prevents thephosphonic groups from assembling therein to further improve storagestability in an aqueous ink.

Therefore, the polymer can be used as a dispersant.

An ink for inkjet recording including the polymer including thestructural units having the formulae (1) and (2), and optionally (3a)and (3b) has good dispersion and storage stability.

Further, when the ink is used on a paper, Ca ions from the paper (evenfrom a plain paper including Ca ions in a small amount) hydrophobize thecopolymer. Further, the structural unit having the formula (2) involvesa pigment and agglutinates to retain the pigment on the paper because ofhaving high adsorptivity to the pigment. Therefore, the resultant imagehas image density.

The structural unit having the formula (3a) is a basic tertiary aminestructure and combined with an acidic group present on the surface of apigment due to acid and base interaction. A hydrosoluble solvent entersan ink vehicle and weakens hydrophobic interaction between a hydrophobicgroup and the pigment. This prevents a resin from lowering itsadsorbability to the pigment and improves pigment dispersibility andstorage stability of an ink including a hydrosoluble solvent. Forexample, a carboxyl group is often present on the surface of carbonblack. The basic tertiary amino group of the structure having theformula (3a) is strongly adsorbed to the surface of a pigment due toacid and base interaction.

The structural unit having the formula (3b) has a quaternary ammoniumbase and combines with an acidic group present on the surface of apigment due to acid and base interaction. A hydrosoluble solvent entersan ink vehicle and weakens hydrophobic interaction between a hydrophobicgroup and the pigment. This prevents a resin from lowering itsadsorbability to the pigment and improves pigment dispersibility andstorage stability of an ink including a hydrosoluble solvent. Forexample, a carboxyl group is often present on the surface of carbonblack. The quaternary ammonium base of the structure having the formula(3b) is strongly adsorbed to the surface of a pigment due to acid andbase interaction.

It is not known exactly why, but copolymerization of the structuralunits having the formulae (1) and (2), and optional (3a) or (3b)prevents phosphonic acid groups from assembling in a polymer to furtherimprove storage stability of an aqueous ink.

The content of the polymer including the structural units having theformulae (1) and (2), and optional (3a) or (3b) in the ink for inkjetrecording is not particularly limited. The ink preferably includes thepolymer in a solid content of from 0.05 to 10% by weight, morepreferably from 0.5 to 5% by weight, and furthermore preferably from 1to 3% by weight. The image density improves when the content is not lessthan 0.05% by weight. When not greater than 10% by weight, the ink hassuitable viscosity when discharged from the inkjet head.

When the polymer including the structural units having the formulae (1)and (2), and optional (3a) or (3b) is used as a pigment, the imagedensity on a plain paper and storage stability of an ink including ahydrosoluble organic solvent much further improve.

The content of the polymer including the structural units having theformulae (1) and (2), and optional (3a) or (3b) is not particularlylimited when used as a pigment dispersant, and preferably from 1 to 100parts by weight, more preferably from 5 to 80 parts by weight, andfurthermore preferably from 10 to 50 parts by weight per 100 parts byweight of the pigment in terms of high image density, and gooddispersion and storage stability.

<Water>

As the water, ion-exchanged water, ultrafiltrated water, Mill-Q water,pure water such as distilled water or ultrapure water can be used.

The content of the water used in the ink for inkjet recording is notparticularly limited.

<Pigment>

Inorganic pigments and organic pigments can be used as the pigment.These can be used alone or in combination.

Specific examples of the inorganic pigments include, but are not limitedto, titanium oxide, iron oxide, calcium carbonate, barium sulfate,aluminum hydroxide, barium yellow, cadmium red, chrome yellow and carbonblack. Among them, the carbon black is preferably used. The carbon blackis produced by known methods such as a contact method, a furnace method,and a thermal method.

Specific examples of the organic pigment include, but are not limitedto, azo pigments, azomethine pigments, polycyclic pigments, dye chelate,a nitro pigment, a nitroso pigment, and aniline black. Among them, theazo pigments and the polycyclic pigments are preferably used.

Specific examples of the azo pigments include, but are not limited to,azo lake, an insoluble azo pigment, a condensed azo pigment, and achelate azo pigment. Specific examples of the polycyclic pigmentsinclude, but are not limited to, a phthalocyanine pigment, a perylenepigment, a perinone pigment, an anthraquinone pigment, a quinacridonpigment, a dioxazine pigment, an indigo pigment, a thioindigo pigment,an iso-indolinone pigment, and a quinophtharone pigment. Specificexamples of the dye chelate include, but are not limited to, basic dyechelate, and an acid dye chelate.

Specific examples of the pigment for black ink include carbon black(C.I. Pigment Black 7) such as furnace black, lamp black, acetyleneblack, and channel black; metals such as copper, iron (C.I. PigmentBlack 11); metal oxides such as titanium oxide; and organic pigmentssuch as aniline black (C.I. Pigment Black 1).

The carbon black preferably has an average primary particle diameter offrom 15 to 40 nm, a BET specific surface area of from 50 to 300 m²/g, aDBP oil absorption of from 40 to 150 mL/100 g, a volatile matter contentof from 0.5 to 10%, and a pH of from 2 to 9.

Specific examples of marketed products of the carbon black include, butare not limited to, Printex 35 and Special Black from Degussa AG.

Specific examples of the pigment for yellow ink include, but are notlimited to, C.I. Pigment Yellow 154 and C.I. Pigment Yellow 174.

Specific examples of the pigment for magenta ink include, but are notlimited to, C.I. Pigment Red 202 and C.I. Pigment Violet 19.

Specific examples of the pigment for cyan ink include, but are notlimited to, C.I. Bat Blue 60.

New pigments may be used in the present invention.

When Pigment Yellow 74 as a yellow pigment, Pigment Red 122 or a PigmentViolet 19 as a magenta pigment and a Pigment Blue 15:3 as a cyan pigmentare used, a well-balanced ink having good color tone and lightresistance can be obtained.

The pigment preferably has a volume-average particle diameter (D50) notgreater than 150 nm, and more preferably not greater than 100 nm toimprove discharge stability and prevent the nozzle from clogging and theink from discharge in a curve.

The volume-average particle diameter (D50) of the pigment us measured byMicrotrac UPA from NIKKISO CO., LTD. in an environment of 23° C. and 55%RH.

The ink preferably includes the pigment in an amount of from 0.1 to 20%by weight, and more preferably from 1 to 20% by weight.

It is preferable that water, a pigment, a dispersant and other optionalcomponents are mixed and dispersed by a disperser to prepare a pigmentdispersion in which a particle diameter thereof is adjusted and that thedispersion is included in the ink.

The pigment dispersion is preferably filtered to remove coarse particlesand deaerated when necessary.

The pigment dispersion preferably includes a pigment in an amount offrom 0.1 to 50% by weight, and more preferably from 0.1 to 30% byweight.

Specific examples of the dispersant include, but are not limited to,surfactants such as anionic surfactants, cationic surfactant, ampholyticsurfactants and nonionic surfactants; sodium naphthalenesulfonateformalin condensates; and polymeric dispersants. These can be used aloneor in combination.

Specific examples of the anionic surfactant include, but are not limitedto, alkylsulfocarboxylic acid salts, α-olefinsulfonic acid salts,polyoxyethylene alkyl ether acetic acid salts, N-acylamino acids orsalts thereof, N-acylmethyltaurine salts, alkylsulfuric acid salts,polyoxyalkyl ether sulfuric acid salts, alkylsulfuric acid salts,polyoxyethylene alkyl ether phosphoric acid salts, rosin acid soap,castor oil sulfate ester salts, lauryl alcohol sulfate ester salts,alkylphenolic phosphate esters, alkylated phosphate esters,alkylarylsulfonic acid salts, diethyl sulfosuccinic acid salts,diethylhexyl sulfosuccinic acid salts, and dioctyl sulfosuccinic acidsalts.

Specific examples of the cationic surfactant include, but are notlimited to, 2-vinylpyridine derivatives and poly-4-vinylpyridinederivatives.

Specific examples of the amphoteric surfactant include, but are notlimited to, betaine lauryldimethylamino acetate,2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, betainecoconut oil fatty acid amidopropyldimethylamino acetate,polyoctylpolyaminoethylglycine, and imidazoline derivatives.

Specific examples of the nonionic surfactant include, but are notlimited to, ether based surfactants such as polyoxyethylene nonylphenylether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecyl phenylether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether,polyoxyethylene lauryl ether and polyoxyethylene alkyl ether; esterbased surfactants such as polyoxyethylene oleate esters, polyoxyethylenedistearate esters, sorbitan laurate, sorbitan monostearate, sorbitanmonooleate, sorbitan sesquioleate, polyoxyethylene monooleate andpolyoxyethylene stearate; acetylene glycol (alcohol) based surfactantssuch as 2,4,7,9-tetramethyl-5-decyne-4,7-diol,3,6-dimethyl-4-octyne-3,6-diol and 3,5-dimethyl-1-hexine-3-ol.

Among these, sodium naphthalenesulfonate formalin condensates arepreferably used.

The sodium naphthalenesulfonate formalin condensates preferably includedimeric, trimeric and tetrameric naphthalenesulfonate in an amount offrom 20 to 80% by weight such that the resultant ink has good viscosityand dispersibility, and improves in storage stability, which preventsthe nozzle form clogging.

<Hydrosoluble Organic Solvent>

The hydrosoluble organic solvent has at least an effect of a wetter or spenetrant.

Specific examples thereof include, but are not limited to polyols suchas glycerin, ethylene glycol, diethylene glycol, isopropylideneglycerol, 1,3-butane diol, 3-methyl-1,3-butane diol, triethylene glycol,propylene glycol, dipropylene glycol, trimethylol propane, trimethylolethane, ethylene glycol, diethylene glycol, dipropylene glycol,tripropylene glycol, tetraethylene glycol, hexylene glycol, polyethyleneglycol, polypropylene glycol, 1,5-pentane diol, 1,6-hexane diol,glycerol, 1,2,6-hexane triol, 1,2,4-butane triol, 1,2,3-butane triol,and petriol; polyol alkyl ethers such as ethylene glycol monoethylether, ethylene glycol monobutyl ether, diethylene glycol monomethylether, diethylene glycol monoethyl ether, diethylene glycol monobutylether, tetraethylene glycol monomethyl ether, and propylene glycolmonoethyl ether; polyol aryl ethers such as ethylene glycol monophenylether, and ethylene glycol monobenzyl ether; nitrogen-containingheterocyclic compounds such as 2-pyrolidone, N-methyl-2-pyrolidone,N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl imidazolidinone,ε-caprolactone, and γ-butyllactone; amides such as formamide,N-methylformamide, N,N-dimethylformamide, N,N-dimethyl-β-methoxy propionamide, and N,N-dimethyl-β-butoxy propion amide; amines such asmonoethanol amine, diethanol amine, triethanol amine, monoethyl amine,diethyl amine, and triethyl amine; sulfur-containing compounds such asdimethyl sulfoxide, sulfolane, and thiodiethanol;3-ethyl-3-hydroxymethyl oxetane, propylene carbonate, and ethylenecarbonate.

Among these solvents, 3-ethyl-3-hydroxymethyloxetane, isopropylideneglycerol, N,N-dimethyl-β-methoxy propion amide, andN,N-dimethyl-β-butoxy propion amide are particularly preferable. Theseeffectively prevent plain papers from curling.

In addition, 1,3-butane diol, diethylene glycol, 2,2,4-trimethyl-1.3-pentanediol, triethyleneglycol and glycerin are effectively used toprevent defective discharge due to moisture evaporation.

Specific examples of the hydrosoluble organic solvent having penetrancemore than wettability include, but are not limited to,2-ethyl-1,3-hexanediol [solubility: 4.2%)(25°)] and2,2,4-trimethyl-1,3-pentanediol [solubility: 2.0%)(25°)].

Specific examples of other polyol compounds include aliphatic diols suchas 2-ethyl-2-methyl-1,3-propanediol, 3,3-dimethyl-1,2-butanediol,2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol,2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol, and5-hexene-1,2-diol.

Other penetrants can be used in combination with the above-mentionedpenetrants as long as the penetrants can be dissolved in the ink, andthe properties of the ink can be controlled so as to fall in the desiredranges. Specific examples thereof include alkyl or aryl ethers ofpolyalcohols such as diethylene glycol monophenyl ether, ethylene glycolmonophenyl ether, ethylene glycol monoallyl ether, diethylene glycolmonobutyl ether, propylene glycol monobutyl ether, and tetraethyleneglycol chlorophenyl ether; and lower alcohols such as ethanol.

Saccharides are also preferable as other solid hydrosoluble organicmaterials.

Specific examples of the saccharides include, but are not limited to,monosaccharides, disaccharides, oligosaccharides (includingtrisaccharides and tetrasaccharides), and polysaccharides. Specificexamples thereof include, but are not limited to, glucose, mannose,fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose,lactose, saccharose, trehalose, and maltotriose. Polysaccharidesrepresent sugar in a broad sense and are materials that are presentwidely in nature, for example, α-cyclodextrine and cellulose. Inaddition, specific examples of derivatives of these saccharides include,but are not limited to, reducing sugars (for example, sugar alcohols(represented by HOCH₂(CHOH)_(n)CH₂OH, where n represents an integer offrom 2 to 5) of the sugar groups specified above, oxidized sugars (e.g.,aldonic acid and uronic acid), amino acid, and thio acid. Among these,sugar alcohols are preferable and specific examples thereof include, butare not limited to, maltitol and sorbit.

The blend ratio of the pigment and the wetter has a large impact on thedischarging stability of ink injected from a head. If the blendingamount of the wetter is too small while the ratio of the solid pigmentportion is high, water evaporation around ink meniscus of nozzles tendsto be accelerated, resulting in bad discharging performance.

The blending ratio of the wetter is preferably from 10 to 60% by weightand more preferably from 20 to 60% by weight based on the ink. The inkhaving such a content ratio is extremely good about the test for drying,preservation, and reliability.

<Other Components>

The ink of the present invention can include other components whennecessary. Specific examples thereof include, but are not limited to, adispersant, a pH adjuster, a water-dispersible resin, an antiseptic andantifungal agent, a chelate reagent, an antirust agent, an antioxidant,an UV absorber, an oxygen absorber, and a light stabilizer.

—Surfactant—

Specific examples the surfactant include, but are not limited to,anionic surfactants, cationic surfactants, nonionic surfactants,ampholytic surfactants and fluorine-containing surfactants. Among these,the nonionic surfactants and the fluorine-containing surfactants arepreferably used.

Specific examples of the anionic surfactants include, but are notlimited to, alkyl allyl, alkylnaphthalene sulfonate, alkyl phosphate,alkyl sulfate, alkyl sulfonate, alkylether sulfate, alkylsulfosuccinate,alkyl ester sulfate, alkylbenzene sulfonate, alkyl diphenyletherdisulfonate, alkyl aryl ether phosphate, alkyl aryl ether sulfate, alkylaryl ether ester sulfate, olefin sulfonate, alkane olefin sulfonate,polyoxyethylenealkylether phosphate, polyoxyethylenealkylether estersalt sulfate, ether carboxylate, sulfosuccinate, α-sulfofatty acidester, fatty acid salts, condensates of higher fatty acid and aminoacid, and naphthenate.

Specific examples of the cationic surfactants include, but are notlimited to, alkylamine salts, dialkylamine salts, aliphatic amine salts,benzalkonium salts, quaternary ammonium salts, alkyl pyridinium slats,imidazolinium salts, sulfonium salts, and phosphonium salts.

Specific examples of the nonionic surfactants include, but are notlimited to, acetylene glycol surfactants, polyoxyethylenealkylether,polyoxyethylenealkylphenylether, polyoxyethylenealkylester, andpolyoxyethylene sorbitan fatty acid ester.

Specific examples of the ampholytic surfactants include, but are notlimited to, imidazoline derivatives such as imidazolinium betaine,dimethyl alkyl lauryl betaine, alkyl glycine, and alkyldi(aminoethyl)glycin.

Specific examples of the fluorine-containing surfactants include, butare not limited to, surfactants having the following formulae (I) to(III):

CF₃CF₂(CF₂CF₂)_(m)—CH₂CH₂O(CH₂CH₂O)_(n)H

wherein each of m represents 0 or an integer of from 1 to 10 and nrepresents 0 or an integer of from 1 to 40.

wherein Rf represents a fluorine-containing group; m, n and p representintegers of from 6 to 25, 1 to 4 and 1 to 4, respectively.

The fluorine containing group is preferably a perfluoroalkyl group. Theperfluoroalkyl group preferably has 1 to 10, and more preferably 1 to 3carbon atoms. Specific examples thereof include, but are not limited to,—C_(n)F_(2n-1) (n is an integer of from 1 to 10) such as —CF₃, —CF₂CF₃,—C₃F₇ and —C₄F₉. Among these, —CF₃ and —CF₂CF₃ are preferable.

wherein Rf represents a fluorine-containing group; R₂ ⁺ represents acationic group; R₁ represents an anionic group; and q is an integer ofform 1 to 6.

The fluorine containing group is preferably a perfluoroalkyl group suchas —CF₃, —CF₂CF₃, —C₃F₇ and —C₄F₉. Specific examples of the cationicgroup include, but are not limited to, a quaternary ammonium group,alkali metal ions such as sodium and potassium, triethylamine andtriethanolamine Among these, the quaternary ammonium group ispreferable. Specific examples of the anionic group include, but are notlimited to, COO⁻. SO₃ ⁻, SO₄ ⁻ and PO₄ ⁻.

Synthesized or marketed fluorine-containing surfactants can be used.

Specific examples of such marketed fluorine-containing surfactantsinclude SARFRONs 5-111, S-112, S-113, S-121, S-131, S-132, S-141 andS-145, which are manufactured by Asahi Glass Co., Ltd.; FLUORADs FC-93,FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430 and FC-431, which aremanufactured by Sumitomo 3M Ltd.; MEGAFACEs F-470, F-1405 and F-474,which are manufactured by DIC Corp.; ZONYLs TBS, FSP, FSA, FSN-100, FSN,FSO-100, FSO, FS-300 and UR, which are manufactured by Du Pont; FT-110,FT-250, FT-251, FT-400S, FT-150 and FT-400SW, which are manufactured byNeos Co., Ltd.; and POLYFOX PF-151N, which is manufactured by Om NovaSolutions, Inc. Among these products, FS-300 (Du Pont); FT-110, FT-250,FT-251, FT-400S, FT-150, and FT-400SW (Neos Co., Ltd.); and POLYFOXPF-151N (Om Nova Solutions, Inc.) are preferable in terms of reliabilityand colorability.

—pH Adjustor—

The pH adjuster is not particularly limited as long as it may adjust apH of the aqueous ink being prepared to 8.5 to 11 without adverselyaffecting the ink. Specific examples of the pH adjuster include, but arenot limited to, alcohol amines, hydroxides of an alkali metal element,hydroxides of ammonium, hydroxides of phosphonium, and carbonates of analkali metal.

Specific examples the alcohol amines include, but are not limited to,diethanolamine, triethanolamine, and 2-amino-2-ethyl-1,3-propanediol.

Specific examples the hydroxides of an alkali metal element include, butare not limited to, lithium hydroxide, sodium hydroxide and potassiumhydroxide.

Specific examples of the hydroxides of ammonium include, but are notlimited to, ammonium hydroxide and quaternary ammonium hydroxide.

Specific examples of the hydroxides of phosphonium include, but are notlimited to, quaternary phosphonium hydroxide.

Specific examples of the carbonates of an alkali metal include, but arenot limited to, lithium carbonate, sodium carbonate and potassiumcarbonate.

—Water-Dispersible Resin—

The water-dispersible resin preferably has good film formability (imageformability), high repellency and high weatherablity to form an imagehaving high repellency and high image density (high colorability).

Specific examples of the water-dispersible resin include, but are notlimited to, condensed synthetic resins such as polyester resins,polyurethane resins, epoxy resins, polyamide resins, polyether resins,(meth)acrylic resins, acrylic-silicone resins and fluorine-containingresins; additional synthetic resins such as polyolefin, polystyreneresins, polyvinylalcohol resins, polyvinyl ester resins, polyacrylicresins and unsaturated carboxylic resins; and natural polymers such ascelluloses, rosins and natural rubbers, which may be used incombination. Among these, polyurethane resin fine particles,acrylic-silicone resin fine particles and fluorine-containing resin fineparticles are preferably used.

A volume-average particle diameter (D50) of the water-dispersible resinis related with a viscosity of a dispersion liquid. The smaller theparticle diameter, the larger the viscosity when the composition is thesame. The volume-average particle diameter (D50) of thewater-dispersible resin is preferably not less than 50 nm so that theink may not have too high a viscosity. When the particle diameter issome ten μm, the resin cannot be used because of being larger than thenozzle of inkjet head. Even when smaller than the nozzle, the large-sizeparticles in the ink deteriorates discharge stability thereof.Therefore, the volume-average particle diameter (D50) of thewater-dispersible resin is more preferably not greater than 200 nm so asnot to impair discharge stability of the ink.

The water-dispersible resin preferably fixes a pigment dispersion on apaper and films it at normal temperature to improve fixability of thepigment.

Therefore, the water-dispersible resin preferably has a minimum filmingtemperature (MFT) not greater than 30° C.

The water-dispersible resin preferably has a glass transitiontemperature not less than −30° C. because the resin film has higherviscosity otherwise, which causes tack of the printed matter.

The ink preferably includes the water-dispersible resin in an amount offrom 1 to 15% by weight, and more preferably from 2 to 7% by weight.

—Antiseptic and Antifungal Agent—

Specific examples the antiseptic and antifungal agent include, but arenot limited to, sodium dehydroacetate, sodium sorbate, 2-pyridinethiol1-oxide sodium, sodium benzoate, and sodium pentachlorophenol.

—Antirust Agent—

Specific examples the antirust agent include, but are not limited to,acid sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammoniumnitrite.

—Antioxidant—

Specific examples of the antioxidant include, but are not limited to, aphenol-based antioxidant (including a hindered phenol-basedantioxidant), an amine-based antioxidant, a sulfur-based antioxidant,and a phosphorus-based antioxidant.

—UV Absorber—

Specific examples of the UV absorber include, but are not limited to, abenzophenone-based UV absorber, a benzotriazole UV absorber, asalicylate-based UV absorber, a cyanoacrylate-based UV absorber, and anickel complex salt-based UV absorber.

<Method of Preparing Ink for Inkjet Recording>

A method of preparing the ink for inkjet recording of the presentinvention includes dispersing or dissolving water, a hydrosolubleorganic solvent, a pigment, a polymer including structural units havingthe formulae (1) and (2), and other optional components in an aqueousmedium to prepare a mixture; and stirring the mixture.

The ink is preferably filtered to remove coarse particles by a filter ora centrifugal separator and deaerated when necessary.

Dispersion can be made by using a sand mill, a homogenizer, a ball mill,a paint shaker, an ultrasonic disperser, and the stirring and mixing canbe made by using ordinary stirring blades, a magnetic stirrer, and ahigh-speed disperser, for example.

<Ink Properties>

Physical properties of the ink of the present invention are notparticularly limited and may be appropriately selected according topurpose.

A viscosity of the aqueous ink at 25° C. is preferably 3 to 20 mPa·s. Aneffect of improved print density and letter quality may be obtained withthe viscosity being 3 mPa·s or greater. At the same time, dischargeproperty may be ensured with the viscosity suppressed to 20 mPa·s orless. The viscosity is measured by a viscometer RE-500L from Toki SangyoCo., Ltd. at 25° C.

(Inkjet Recording Method and Inkjet Recorder)

The inkjet recorder of the present invention records information or animage on a recording medium with the ink of the present invention usingan inkjet head. The recorder has least an ink flight means discharging,and other means such as a stimulation generator and a controller whennecessary.

The ink flight means is a means of applying a stimulation to the ink ofthe present invention to fly to form a an image. The ink flight meansinclude, but are not limited to, various nozzles for discharging inks.

The stimulation is generated by, e.g., a stimulation generator. Specificexamples of the stimulation include, but are not limited to, heat(temperature), pressure, oscillation and light. These can be used aloneor in combination. Among these, heat and pressure are preferably used.Specific examples of the stimulation generator include, but are notlimited to, heaters, pressurizers, piezo elements, oscillators,ultrasonic oscillators, and lights. For example, piezo actuator such aspiezo element, thermal actuator using a phase variation due to filmboiling of a liquid using electric heat conversion element such asheating resistant, shape-memory alloy actuator using metal phasevariation due to variation of temperature, electrostatic actuator usingelectrostatic force are used.

The controller is not particularly limited as long as it is capable ofcontrolling operation of each of the means, and includes a sequencer, acomputer, etc.

(Ink Container)

The ink container of the present invention contains the inkjet ink ofthe present invention and may include any other suitable members incombination.

There is no specific limit to the container. Any form, any structure,any size, and any material can be suitably selected. For example, an inkbag formed of aluminum laminate film, a resin film, etc. can be suitablyused as a container.

FIG. 1 is a schematic plain view illustrating an embodiment of the inkcontainer 200 of the present invention. FIG. 2 is a schematic plain viewillustrating the embodiment of the ink container 200 including a case(outer package) in FIG. 1.

As illustrated in FIG. 1, an ink bag 241 is filled with the ink from anink inlet 242. Subsequent to evacuation of air, the ink inlet 242 isclosed by fusion. When in use, the ink is supplied by piercing theneedle attached to the inkjet recorder into an ink outlet 243 made ofrubber. The ink bag 241 is formed of a packaging material such asaluminum laminate film having no air permeability. The ink bag 241 isaccommodated in a cartridge case 244 made of plastic as illustrated inFIG. 4 and detachably attachable to various inkjet recorders.

Inkjet recorders include inkjet printers, facsimile machines,photocopiers, multi-functional machines (serving as a printer, afacsimile machine, and a photocopier), etc.

Specific examples of recording media recorded by the inkjet recorderinclude, but are not limited to, plain papers, coated papers forprinting, glossy paper, special papers, clothes, films and OHP sheets.

FIG. 3 is a perspective view illustrating an embodiment of the inkjetrecorder of the present invention.

An inkjet recorder 101 illustrated in FIG. 3 has a sheet feeder tray 102to feed recording media placed in the inkjet recorder 101, a dischargingtray 103 installed in the inkjet recorder 101, which stores therecording media on which images are recorded (formed), and an inkcartridge installation unit 104. On the upper surface of the inkcartridge installation unit 104 is arranged an operating portion 105including operation keyboard, a display, etc. The ink cartridgeinstallation unit 104 has a front cover 115 that is openable andclosable to detach and attach an ink container 200. 111 represents theupper cover of the inkjet recorder 101 and 112 represents the frontsurface thereof.

Inside the inkjet recorder 101, as illustrated in FIGS. 4 and 5, a guiderod 131 and a stay 132 serving as guiding members that laterally bridgeside plates provided on the right side and left side hold a carriage 133slidably movable in the main scanning direction. A main scanning motormoves the carriage 133 for scanning in an arrow direction in FIG. 5.

The carriage 133 has a recording head 134 having four inkjet recordingheads that discharge ink droplets of each color of yellow (Y), cyan (C),magenta (M), and black (Bk) while multiple ink discharging mouths arearranged in the direction crossing the main scanning direction with theink droplet discharging direction downward.

As the heads for inkjet recording that form the recording head 134, itis possible to use a device having an energy-generating device todischarge ink such as a piezoelectric actuator such as a piezoelectricelement, a thermal actuator that utilizes the phase change caused byfilm boiling of liquid using an electric heat conversion element such asa heat element, a shape-memory alloy actuator that uses the metal phasechange due to the temperature change, and an electrostatic actuator thatuses an electrostatic force. The carriage 133 has a sub tank 135 foreach color to supply each color ink to the recording head 134. The inkis supplied and replenished to the sub-tank 135 from the ink container200 mounted onto the ink cartridge inserting installation unit 104 via atube for supplying ink.

A sheet feeding unit to feed a sheet 142 loaded on a sheet loader(pressure plate) 141 of the sheet feeder tray 103 includes a roller(sheet feeding roller 143) having a half-moon like form to separate andfeed the sheet 142 one by one from the sheet loader 141 and a separationpad 144 that is made of a material having a large friction index andarranged facing the sheet feeding roller 143 while biased to the side ofthe sheet feeding roller 143.

A transfer unit to transfer the sheet 142 fed from the sheet feedingunit on the lower side of the recording head 134 includes a transferbelt 151 to electrostatically adsorb and transfer the sheet 142, acounter roller 152 to transfer the sheet 142 fed from the sheet feedingunit via a guide 145 while pinching the sheet 142 with the transfer belt151, a transfer guide 153 to make the sheet 142 track on the transferbelt 151 by changing the transfer direction of the sheet 142 being sentsubstantially vertically upward by substantially 90°, a front headpressure roller 155 biased towards the transfer belt 151 by a pressuremember 154, and a charging roller 156 to charge the surface of thetransfer belt 151.

The transfer belt 151 is an endless form belt, stretched between atransfer roller 157 and a tension roller 158 and rotatable in the belttransfer direction. This transfer belt 151 include, for example, a toplayer serving as a sheet adsorption surface made of a resin materialsuch as a copolymer (ETFE) of tetrafluoroethylene and ethylene with noresistance control treatment while having a thickness about 40 μm, and abottom layer (moderate resistance layer, earth layer) made of the samematerial as the top layer with resistance control treatment with carbon.On the rear side of the transfer belt 151, a guiding member 161 isarranged corresponding to the printing area by the recording head 134.

A discharging unit to discharge the sheet 142 on which images arerecorded by the recording head 134 includes a separation claw 171 toseparate the sheet 142 from the transfer belt 151, a discharging roller172, and a discharging roller 173. A discharging tray 103 is arrangedbelow the discharging roller 172.

A duplex printing sheet feeding unit 181 is detachably attached to therear side of the inkjet recorder 101. The duplex printing sheet feedingunit 181 takes in and reverses the sheet 142 that is returned by thereverse rotation of the transfer belt 151 and feeds it again between thecounter roller 152 and the transfer belt 151. A manual sheet feedingunit 182 is provided on the upper surface of the duplex printing sheetfeeding unit 181.

In this inkjet recorder, the sheet 142 is separated and fed from thesheet feeding unit one by one substantially vertically upward, guided bythe guide 145, and transferred while being pinched between the transferbelt 151 and the counter roller 152. Furthermore, the front end of thesheet 142 is guided by the transfer guide 153 and pressed against thetransfer belt 151 by the front head pressure roller 155 to change thetransfer direction by substantially 90°. Since the transfer belt 157 ischarged by the charging roller 156 at this point in time, the sheet 142is electrostatically adsorbed to the transfer belt 151 and transferred.By driving the recording head 134 according to the image signal whilemoving the carriage 133, the ink droplet is discharged to the sheet 142not in motion to record an image for an amount corresponding to one lineand thereafter the sheet 142 is transferred in a predetermined amount toconduct recording for the next line.

On receiving a signal indicating that the recording has completed or therear end of the sheet 142 has reached the image recording area, therecording operation stops and the sheet 142 is discharged to thedischarging tray 103. When the amount of ink for inkjet recordingremaining in the sub-tank 135 is detected as “approaching to empty”, apredetermined amount of the ink is replenished to the sub tank 135 fromthe ink container 200.

In this inkjet recorder, it is possible to dissemble the chassis of theink container 200 and replace the ink bags therein when the ink forinkjet is used up in the ink container 200. In addition, the inkcartridge 200 stably supplies the ink even when the ink cartridge 200 isplaced upright (on its side) and installed by front loading. Therefore,even when the upside of the main part 101 is blocked, for example, it isaccommodated in a rack or something is placed on the upper surface ofthe main part 101, the ink cartridge 200 is easily exchanged.

A serial type (shuttle type) in which the carriage scans is used in thisdescription but this is true in a line-type inkjet recorder having aline type head.

The inkjet recorder is applicable to various inkjet recordings such asinkjet recording printers, facsimiles, copiers and their combinationmachines.

The recorded matter of the present invention is recorded by the inkjetrecording method of the present invention, and has an image recorded bythe inkjet ink of the present invention on a recording medium.

The recording media are not particularly limited, as long as the inkjetrecording ink of the present invention lands thereon to form an imagethereon. Specific examples thereof includes plain papers, coated papersfor printing, glossy papers, special papers, etc. They include calciumcarbonate, talc, kaolin or aluminum sulfate, etc., and divalent ortrivalent ions such as calcium, magnesium and aluminum elute when theinkjet recording ink of the present invention lands thereon.

Plain papers are preferably used in the present invention. The plainpapers are whole paper media supporting images, having feedability andtransferability in image forming apparatuses for office use, home use orpersonal use using hard copy forming technologies such aselectrophotographic copiers, simple offset printers, printers or olddiazo copiers. Plain papers are mostly quality papers recently.Therefore, quality papers are often called plain papers, and a typicalimage medium for electrophotographic method as an image formingtechnology is familiarly known as PPC (plain paper copy).

The ink of the present invention reacts with the metallic ions toagglutinate a pigment and produces images having high image density.However, the plain papers are difficult to have high image density.

Most of loading materials and size fixers included in the plain papersare metallic salts having poor water solubility. Even when awater-soluble metallic salt is included, the content there of is low.Therefore, the plain papers do not improve in image density so much aspapers including water-soluble multivalent metallic salts.

However, the inkjet recording ink of the present invention reacts with apigment to produce images having high image density even when themultivalent metallic ions elute less. Specific examples of the marketedplain papers include quality paper My Paper from Ricoh Company, Ltd.,Xerox 4024 from Fuji Xerox Co, Ltd., etc.

The ink of the present invention is effectively used on a paper elutingCa ion in an amount of from 1.0×10⁻⁴ to 5.0×10⁻⁴ g/g. When less than1.0×10⁻⁴ g/g, improvement of the image density due to reactionagglomeration with the pigment dispersant deteriorates. When greaterthan 5.0×10⁻⁴ g/g, an ink noticeably becomes difficult to penetrate apaper and poorly dried, resulting in deterioration of scratch resistanceand marker resistance.

Ca ion amount eluted from a paper is calculated by the following method.

Namely, a paper is cut to paper slips of 2.5 cm (±0.5 cm)×3.5 cm (±0.5cm), and 16 g thereof are dipped in 200 g of high-purity water (25° C.)for 40 hrs. The high-purity water after the paper slips are dippedtherein is filtered with a 0.8 μm cellulose acetate filter (fromAdvantech Co., Ltd.) to remove foreign particles such as paper dusts,and Ca ion included therein is determined by an ICP emissionspectrometer. The resultant Ca ion concentration [ppm] is multiplied by200 g which is the weight of the high-purity water, and further dividedby 16 g which is the weight of the paper dipped to determine an amountof Ca ion [g/g] eluted from the paper.

For example, My Paper from Ricoh Company, Ltd. includes Ca ion in anamount of 4.3×10⁻⁴ g/g, and Xerox 4024 from Fuji Xerox Co, Ltd. includesCa ion in an amount of 1.7×10⁻⁴ g/g.

EXAMPLES

Having generally described this invention, further understanding can beobtained by reference to certain specific examples which are providedherein for the purpose of illustration only and are not intended to belimiting. In the descriptions in the following examples, the numbersrepresent weight ratios in parts, unless otherwise specified.

Synthesis of Monomer Monomer No. I-1: Sodium1-hydroxy-4-methacrylamidebutane-1,1-diylbis(hydrogenphosphonate)

In a flask, 25 parts of alendronic acid from Tokyo Chemical IndustryCo., Ltd. were placed, and an aqueous solution including 17.1 parts ofsodium hydroxide and 200 parts of ion-exchanged water was placed thereinto be completely dissolved while stirred. Next, 13.32 parts ofmethacrylic acid chloride from Tokyo Chemical Industry Co., Ltd. wereslowly dropped therein while cooled at 5° C. After stirred for 30 min,14.53 parts of concentrated hydrochloric acid were dropped therein whilecooled. The reacted liquid was extracted and washed for 3 times withmethylene chloride, and the remaining aqueous solution was dropped in800 parts of methanol and filtered to extract 35 parts of an object.

One point seven (1.7) parts of the object were dissolved in 176 parts ofion-exchanged water to prepare a solution, and the solution wassubjected to neutralization titration in 0.1 N of KOH methanol solutionwith thymolphthalein from Kanto Chemical Co., Inc. as an indicator todetermine an acid value. The acid value was 155 mg KOH/g. Compared withthe titration result of the alendronic acid, the acid value was the samewhen 2 OH groups were replaced with Na salts.

Monomer No. I-2: Potassium1-hydroxy-4-methacrylamidebutane-1,1-diylbis(hydrogenphosphonate)

The procedure for preparation of the object in synthesis of Monomer No.1 was repeated except for replacing 17.1 parts of sodium hydroxide with24 parts of potassium hydroxide to prepare 40 parts of an object.

Monomer No. I-3: Sodium4-acrylamide-1-hydroxybutane-1,1-diylbis(hydrogenphosphonate)

The procedure for preparation of the object in synthesis of Monomer No.1 was repeated except for replacing 13.32 parts of methacrylic acidchloride with 11.53 parts of acrylic acid chloride from Tokyo ChemicalIndustry Co., Ltd. to prepare 33 parts of an object.

Monomer No. I-4: Triethylammonium4-acrylamide-1-hydroxybutane-1,1-diylbis(hydrogenphosphonate)

The procedure for preparation of the object in synthesis of Monomer No.1 was repeated except for replacing 13.32 parts of methacrylic acidchloride with 11.53 parts of acrylic acid chloride, and 17.1 parts ofsodium hydroxide with 43.3 parts of triethylamine from Kanto ChemicalCo., Inc. to prepare 44 parts of an object.

Monomer No. I-5: Tetraethylammonium 1-hydroxy-4-methacrylamidebutane1,1-diylbis(hydrogenphosphonate)

The procedure for preparation of the object in synthesis of Monomer No.1 was repeated except for replacing 17.1 parts of sodium hydroxide with179.8 parts of tetraethylammonium hydroxide (35% aqueous solution) fromKanto Chemical Co., Inc., and 200 parts of ion-exchanged water with 83.1parts thereof to prepare 55 parts of an object.

Monomer No. I-6: Tetraethylammonium 1-hydroxy-4-methacrylamidebutane1,1-diylbis(hydrogenphosphonate)

The procedure for preparation of the object in synthesis of Monomer No.1 was repeated except for replacing 17.1 parts of sodium hydroxide with277.2 parts of tetraethylammonium hydroxide (40% aqueous solution) fromKanto Chemical Co., Inc., and 200 parts of ion-exchanged water with 33.7parts thereof to prepare 76 parts of an object.

Synthesis Example I-1 Copolymer (Polymer 1) Including a Salt ofPhosphonic Acid Group

In a reaction container including a gas inlet tube, a thermometer and areflux condenser, in an argon atmosphere, 450 parts ofN-dimethylformamide (DMF) were placed and heated at 75° C. In thecontainer, 558 parts of aqueous solution including 75 parts of themonomer No. I-1 as the monomer having the formula (4), 525 parts of aDMF solution including 75 parts of cyclohexylmethacrylate as the monomerhaving the formula (5), and 464 parts of a DMF solution including 4.5parts of 2,2′-azobisisobutylonitrile (AIBN) and 9 parts ofα-thioglycerol were added in 12 batches every 30 min. After these wereall added therein, the mixture was further stirred for 4 hrs, cooled andthe polymerization was completed.

The extract was filtered, washed with hexane, and dried to obtain 136parts of a copolymer (polymer I-1).

One (1) part of the resin (copolymer) was dissolved in 120 parts ofion-exchanged water to prepare a solution, and the solution wassubjected to neutralization titration in 0.1 N of KOH methanol solutionwith thymolphthalein as an indicator to determine an acid value. Theacid value was 78 mg KOH/g. This was almost same as 77.7 mg KOH/gdetermined from the acid value of the monomer No. I-1 assumingcopolymerization had been made in proportion to the place-in quantity.

Based on the acid value, the copolymer was neutralized with sodiumhydroxide to prepare an aqueous solution including 10% by weight of theresin. The solution had a viscosity of 1.84 mPa·s at 25° C.

The aqueous solution including 10% by weight of the resin was used forpreparing a pigment dispersion. From the titration result of thealendronic acid (monomer material), 3 OH groups out of 4 of thephosphonic acid were proved to be neutralized by sodium ion. The resultsare shown in Table I-1.

Synthesis Examples I-2 Polymer I-2

The procedure for preparation of the polymer I-1 in Synthesis ExampleI-1 was repeated except for changing the monomers having the formulae(4) and (5) and the conditions as shown in Table I-1 to prepare polymerI-2. The copolymer was neutralized with potassium hydroxide to preparean aqueous solution including 10% by weight of the resin. The solutionhad a viscosity of 1.82 mPa·s at 25° C. Three (3) OH groups out of 4 ofthe phosphonic acid were proved to be neutralized by sodium ion. Theresults are shown in Table I-1.

Synthesis Examples I-3 (Polymer I-3) to I-31 (Polymer I-33) andComparative Synthesis Examples I-1 (Polymer I-34) to I-2 (Polymer I-35)

The procedure for preparation of the polymer I-1 in Synthesis ExampleI-1 was repeated except for changing the monomers having the formulae(4) and (5) and the conditions as shown in Table I-1 to prepare polymersI-3 to I-33.

Comparative Synthesis Example I-3 Preparation of Neutralization Salt of2-hydroxyethylidenediphosphonic Acid

2-hydroxyethylidene-1,1-diphosphonic acid was neutralized by 2equivalents of potassium hydroxide in methanol, and the methanol wasremoved.

An aqueous solution including 10% by weight of a salt of the2-hydroxyethylidene-1,1-diphosphonic acid had a viscosity of 1.9 mPa·sat 25° C.

TABLE I-1 (1) Polymer Structural Unit Monomer (4) Monomer (5) Polymer %by % by Syn. Ex. No. Polymer No. Name weight Name weight Syn. Ex. I-1Polymer I-1 Monomer 50 Cyclohexyl MA 50 No. I-1 Syn. Ex. I-2 Polymer I-2Monomer 50 Cyclohexyl MA 50 No. I-2 Syn. Ex. I-3 Polymer I-3 Monomer 50Dodecyl Ma 50 No. I-1 Syn. Ex. I-4 Polymer I-4 Monomer 50 Dodecyl Ma 50No. I-2 Syn. Ex. I-5 Polymer I-5 Monomer 50 Hexadecanyl Ma 50 No. I-1Syn. Ex. I-6 Polymer I-6 Monomer 50 Hexadecanyl Ma 50 No. I-2 Syn. Ex.I-7 Polymer I-7 Monomer 50 Octadecanyl MA 50 No. I-1 Syn. Ex. I-8Polymer I-8 Monomer 50 Octadecanyl MA 50 No. I-2 Syn. Ex. I-9 PolymerI-9 Monomer 50 Docosanyl MA 50 No. I-1 Syn. Ex. I-10 Polymer I-10Monomer 50 Docosanyl MA 50 No. I-2 Syn. Ex. I-11 Polymer I-11 Monomer 25Benzyl MA 75 No. I-1 Syn. Ex. I-12 Polymer I-12 Monomer 30 Benzyl MA 70No. I-1 Syn. Ex. I-13 Polymer I-13 Monomer 40 Benzyl MA 60 No. I-1 Syn.Ex. I-14 Polymer I-14 Monomer 50 Benzyl MA 50 No. I-1 Syn. Ex. I-15Polymer I-15 Monomer 60 Benzyl MA 40 No. I-1 Syn. Ex. I-16 Polymer I-16Monomer 70 Benzyl MA 30 No. I-1 Syn. Ex. I-17 Polymer I-17 Monomer 75Benzyl MA 25 No. I-1 Syn. Ex. I-18 Polymer I-18 Monomer 50 Benzyl A 50No. I-1 Syn. Ex. I-19 Polymer I-19 Monomer 60 Dodecyl A 40 No. I-1 Syn.Ex. I-20 Polymer I-20 Monomer 60 Hexadecanyl A 40 No. I-1 Syn. Ex. I-21Polymer I-21 Monomer 60 Octadecanyl A 40 No. I-1 Syn. Ex. I-22 PolymerI-22 Monomer 60 Benzyl MA 40 No. I-3 Syn. Ex. I-23 Polymer I-23 Monomer50 Dodecyl MA 50 No. I-3 Syn. Ex. I-24 Polymer I-24 Monomer 60Octadecanyl MA 40 No. I-3 Syn. Ex. I-25 Polymer I-25 Monomer 40 Benzyl A60 No. I-3 Syn. Ex. I-26 Polymer I-26 Monomer 50 Benzyl A 50 No. I-4Syn. Ex. I-27 Polymer I-27 Monomer 60 Benzyl A 40 No. I-3 Syn. Ex. I-28Polymer I-28 Monomer 50 Benzyl A 50 No. I-3 Syn. Ex. I-29 Polymer I-29Monomer 50 Benzyl A 50 No. I-3 Syn. Ex. I-30 Polymer I-30 Monomer 50Benzyl A 50 No. I-3 Syn. Ex. I-31 Polymer I-31 Monomer 50 Benzyl A 50No. I-3 Syn. Ex. I-32 Polymer I-32 Monomer 50 Benzyl A 50 No. I-5 Syn.Ex. I-33 Polymer I-33 Monomer 50 Benzyl A 50 No. I-6 Com. Syn. PolymerI-34 Monomer 100 — 0 Ex. I-1 No. I-1 Com. Syn. Polymer I-35 Monomer 502- 50 Ex. I-2 No. I-2 hydroxypropylacrylamide (2) DMF Polymer ViscosityM in placement Monomer (1) Syn. Ex. No. Polymer No. (mPa · s) formula(1) Parts by Wt. Parts by Wt. Syn. Ex. I-1 Polymer I-1 1.84 3Na, 1H 45075 Syn. Ex. I-2 Polymer I-2 1.82 3K, 1H 450 75 Syn. Ex. I-3 Polymer I-31.86 2Na, 2H 450 75 Syn. Ex. I-4 Polymer I-4 1.84 2K, 2H 450 75 Syn. Ex.I-5 Polymer I-5 2.18 3Na, 1H 450 75 Syn. Ex. I-6 Polymer I-6 2.16 3K, 1H450 75 Syn. Ex. I-7 Polymer I-7 2.20 3Na, 1H 450 75 Syn. Ex. I-8 PolymerI-8 2.17 3K, 1H 450 75 Syn. Ex. I-9 Polymer I-9 3.87 3Na, 1H 200 75 Syn.Ex. I-10 Polymer I-10 3.85 3K, 1H 200 75 Syn. Ex. I-11 Polymer I-11 2.123Na, 1H 450 375 Syn. Ex. I-12 Polymer I-12 2.13 3Na, 1H 450 45 Syn. Ex.I-13 Polymer I-13 2.16 3Na, 1H 450 60 Syn. Ex. I-14 Polymer I-14 2.183Na, 1H 450 75 Syn. Ex. I-15 Polymer I-15 2.21 3Na, 1H 450 90 Syn. Ex.I-16 Polymer I-16 2.23 3Na, 1H 450 105 Syn. Ex. I-17 Polymer I-17 2.243Na, 1H 450 112.5 Syn. Ex. I-18 Polymer I-18 1.90 3Na, 1H 450 75 Syn.Ex. I-19 Polymer I-19 1.90 3Na, 1H 450 90 Syn. Ex. I-20 Polymer I-201.92 3Na, 1H 450 90 Syn. Ex. I-21 Polymer I-21 1.94 3Na, 1H 450 90 Syn.Ex. I-22 Polymer I-22 1.93 3Na, 1H 450 90 Syn. Ex. I-23 Polymer I-232.51 3Na, 1H 450 75 Syn. Ex. I-24 Polymer I-24 2.56 3Na, 1H 450 90 Syn.Ex. I-25 Polymer I-25 2.55 3Na, 1H 450 60 Syn. Ex. I-26 Polymer I-262.50 2TEtA, 2H 450 75 Syn. Ex. I-27 Polymer I-27 1.67 3Na, 1H 450 90Syn. Ex. I-28 Polymer I-28 1.42 3Na, 1H 450 75 Syn. Ex. I-29 PolymerI-29 1.50 3Na, 1H 450 75 Syn. Ex. I-30 Polymer I-30 4.00 3Na, 1H 200 75Syn. Ex. I-31 Polymer I-31 4.27 3Na, 1H 200 75 Syn. Ex. I-32 PolymerI-32 2.13 3TetraEtA, 1H 450 75 Syn. Ex. I-33 Polymer I-33 2.113TetraBuA, 1H 450 75 Com. Syn. Polymer I-34 3.50 3Na, 1H 900 150 Ex. I-1Com. Syn. Polymer I-35 3.96 2K, 2H 200 75 Ex. I-2 (3) Monomer (1)Monomer (2) Aqueous DMF Polymer Solution Monomer (2) solution AIBN Syn.Ex. No. Polymer No. Parts by Wt. Parts by Wt. Parts by Wt. Parts by Wt.Syn. Ex. I-1 Polymer I-1 558 75 525 4.5 Syn. Ex. I-2 Polymer I-2 558 75525 4.5 Syn. Ex. I-3 Polymer I-3 558 75 525 4.5 Syn. Ex. I-4 Polymer I-4558 75 525 4.5 Syn. Ex. I-5 Polymer I-5 558 75 525 4.5 Syn. Ex. I-6Polymer I-6 558 75 525 4.5 Syn. Ex. I-7 Polymer I-7 558 75 525 4.5 Syn.Ex. I-8 Polymer I-8 558 75 525 4.5 Syn. Ex. I-9 Polymer I-9 275 75 2594.5 Syn. Ex. I-10 Polymer I-10 275 75 259 4.5 Syn. Ex. I-11 Polymer I-11521 112.5 563 13.5 Syn. Ex. I-12 Polymer I-12 528 105 555 13.5 Syn. Ex.I-13 Polymer I-13 543 90 540 13.5 Syn. Ex. I-14 Polymer I-14 558 75 52513.5 Syn. Ex. I-15 Polymer I-15 573 60 510 13.5 Syn. Ex. I-16 PolymerI-16 588 45 495 13.5 Syn. Ex. I-17 Polymer I-17 596 37.5 488 13.5 Syn.Ex. I-18 Polymer I-18 558 75 525 18 Syn. Ex. I-19 Polymer I-19 573 60510 18 Syn. Ex. I-20 Polymer I-20 573 60 510 18 Syn. Ex. I-21 PolymerI-21 573 60 510 18 Syn. Ex. I-22 Polymer I-22 573 60 510 18 Syn. Ex.I-23 Polymer I-23 558 75 525 4.5 Syn. Ex. I-24 Polymer I-24 573 60 5104.5 Syn. Ex. I-25 Polymer I-25 543 90 540 4.5 Syn. Ex. I-26 Polymer I-26558 75 525 4.5 Syn. Ex. I-27 Polymer I-27 573 60 510 9 Syn. Ex. I-28Polymer I-28 558 75 525 13.5 Syn. Ex. I-29 Polymer I-29 558 75 525 9Syn. Ex. I-30 Polymer I-30 275 75 259 4.5 Syn. Ex. I-31 Polymer I-31 27575 259 3 Syn. Ex. I-32 Polymer I-32 558 75 525 14 Syn. Ex. I-33 PolymerI-33 558 75 525 14 Com. Syn. Polymer I-34 633 0 0 13.5 Ex. I-1 Com. Syn.Polymer I-35 275 75 259 4.5 Ex. I-2 (4) AIBN DMF Polymerization PolymerThioglycerol solution Temperature Polymer Syn. Ex. No. Polymer No. Partsby Wt. Parts by Wt. (° C.) Parts by Wt. Syn. Ex. I-1 Polymer I-1 9 46475 136 Syn. Ex. I-2 Polymer I-2 9 464 75 136 Syn. Ex. I-3 Polymer I-3 9464 75 136 Syn. Ex. I-4 Polymer I-4 9 464 75 136 Syn. Ex. I-5 PolymerI-5 4.5 459 75 138 Syn. Ex. I-6 Polymer I-6 4.5 459 75 138 Syn. Ex. I-7Polymer I-7 4.5 459 75 138 Syn. Ex. I-8 Polymer I-8 4.5 459 75 138 Syn.Ex. I-9 Polymer I-9 0 194 75 147 Syn. Ex. I-10 Polymer I-10 0 194 75 147Syn. Ex. I-11 Polymer I-11 0 464 75 142 Syn. Ex. I-12 Polymer I-12 0 46475 142 Syn. Ex. I-13 Polymer I-13 0 464 75 142 Syn. Ex. I-14 PolymerI-14 0 464 75 142 Syn. Ex. I-15 Polymer I-15 0 464 75 142 Syn. Ex. I-16Polymer I-16 0 464 75 142 Syn. Ex. I-17 Polymer I-17 0 464 75 142 Syn.Ex. I-18 Polymer I-18 0 468 75 140 Syn. Ex. I-19 Polymer I-19 0 468 75140 Syn. Ex. I-20 Polymer I-20 0 468 75 140 Syn. Ex. I-21 Polymer I-21 0468 75 140 Syn. Ex. I-22 Polymer I-22 0 468 75 140 Syn. Ex. I-23 PolymerI-23 1.5 456 75 142 Syn. Ex. I-24 Polymer I-24 1.5 456 75 142 Syn. Ex.I-25 Polymer I-25 1.5 456 75 142 Syn. Ex. I-26 Polymer I-26 1.5 456 75142 Syn. Ex. I-27 Polymer I-27 12 471 90 130 Syn. Ex. I-28 Polymer I-2812 476 90 123 Syn. Ex. I-29 Polymer I-29 12 471 90 130 Syn. Ex. I-30Polymer I-30 0 194 75 147 Syn. Ex. I-31 Polymer I-31 0 192 75 148 Syn.Ex. I-32 Polymer I-32 0 464 75 140 Syn. Ex. I-33 Polymer I-33 0 464 75142 Com. Syn. Polymer I-34 0 464 75 142 Ex. I-1 Com. Syn. Polymer I-35 0194 75 147 Ex. I-2

3Na. 1H represents M+ includes 3 Na ions and 1 proton. 2K, 2H represents2 K ions and 2 protons. TEtA represents trimethylammonium ion. TetraEtArepresents tetraethylammonium ion and TetraBuA representstetrabutylammonium ion. MA represents methacrylate and A representsacrylate.

Preparation of Pigment Dispersion Pigment Dispersion Preparation ExampleI-1

The following materials were premixed, subjected to a circulationdispersion by a disc type beads mill (KDL type from Shinmaru EnterprisesCorp., using zirconia beads having a diameter of 0.1 mm) at a peripheralspeed of 10 m/s for 10 min, and filtered with a membrane filter havingan aperture of 1.2 μm to prepare a pigment dispersion I-1.

[Mixture I-1]

Carbon black (NIPEX160 from Degussa AG) 20.0 Naphthalene sulfonic acidNa formalin condensate 13.0 (including a solid content of 10% by weight)Pure water 67.0

Pigment Dispersion Preparation Example I-2

The procedure for preparation of the pigment dispersion 1 in PigmentDispersion Preparation Example 1 was repeated except for replacing the[Mixture I-1] with the following [Mixture I-2] to prepare a pigmentdispersion I-2.

[Mixture I-2]

Carbon black (NIPEX150 from Degussa AG) 20.0 Polymer 1 (including asolid content of 10% by weight) 50.0 Pure water 30.0

Pigment Dispersion Preparation Examples I-3 to I-40

The procedure for preparation of the pigment dispersion I-1 in PigmentDispersion Preparation Example 1 was repeated except for replacing the[Mixture I-1] with the mixtures shown in Table I-2 to prepare pigmentdispersions I-3 to I-40. The pigment dispersion 1 includes naphthalenesulfonic acid Na formalin condensate, but the pigment dispersions I-2 toI-40 do not. The pigment dispersion 38 does not include a copolymer(polymer) including a salt of phosphonic acid group, and includes alow-molecular-weight bisphosphonic acid.

TABLE I-2 (1) Solid Content Pigment Dispersion (%) I-1 I-2 I-3 I-4 I-5Naphthalene 10 13 sulfonic acid Na formalin condensate Polymer I-1 10 50Polymer I-2 10 50 Polymer I-3 10 50 Polymer I-4 10 50 Polymer I-5 10Polymer I-6 10 Polymer I-7 10 Polymer I-8 10 Polymer I-9 10 Polymer I-1010 Polymer I-11 10 Polymer I-12 10 Polymer I-13 10 Polymer I-14 10Polymer I-15 10 Polymer I-16 10 Polymer I-17 10 Polymer I-18 10 PolymerI-19 10 Polymer I-20 10 Polymer I-21 10 Polymer I-22 10 Polymer I-23 10Polymer I-24 10 Polymer I-25 10 Polymer I-26 10 Polymer I-27 10 PolymerI-28 10 Polymer I-29 10 Polymer I-30 10 Polymer I-31 10 Polymer I-32 10Polymer I-33 10 Polymer I-34 10 Polymer I-35 10 1-hydroxyethylidene-1,1-10 bisphosphonic acid Carbon black (*1) — 20 20 20 20 20 Pigment Blue15:3 (*2) Pigment Red 122 (*3) — Pigment Yellow 74 (*4) — Pure water —67 30 30 30 30 Total — 100 100 100 100 100 (2) Solid Content PigmentDispersion (%) I-6 I-7 I-8 I-9 I-10 Naphthalene 10 sulfonic acid Naformalin condensate Polymer I-1 10 Polymer I-2 10 Polymer I-3 10 PolymerI-4 10 Polymer I-5 10 50 Polymer I-6 10 50 Polymer I-7 10 50 Polymer I-810 50 Polymer I-9 10 50 Polymer I-10 10 Polymer I-11 10 Polymer I-12 10Polymer I-13 10 Polymer I-14 10 Polymer I-15 10 Polymer I-16 10 PolymerI-17 10 Polymer I-18 10 Polymer I-19 10 Polymer I-20 10 Polymer I-21 10Polymer I-22 10 Polymer I-23 10 Polymer I-24 10 Polymer I-25 10 PolymerI-26 10 Polymer I-27 10 Polymer I-28 10 Polymer I-29 10 Polymer I-30 10Polymer I-31 10 Polymer I-32 10 Polymer I-33 10 Polymer I-34 10 PolymerI-35 10 1-hydroxyethylidene-1,1- 10 bisphosphonic acid Carbon black (*1)— 20 20 20 20 20 Pigment Blue 15:3 (*2) Pigment Red 122 (*3) — PigmentYellow 74 (*4) — Pure water — 30 30 30 30 30 Total — 100 100 100 100 100(3) Solid Content Pigment Dispersion (%) I-11 I-12 I-13 I-14 I-15Naphthalene 10 sulfonic acid Na formalin condensate Polymer I-1 10Polymer I-2 10 Polymer I-3 10 Polymer I-4 10 Polymer I-5 10 Polymer I-610 Polymer I-7 10 Polymer I-8 10 Polymer I-9 10 Polymer I-10 10 50Polymer I-11 10 50 Polymer I-12 10 50 Polymer I-13 10 50 Polymer I-14 1050 Polymer I-15 10 Polymer I-16 10 Polymer I-17 10 Polymer I-18 10Polymer I-19 10 Polymer I-20 10 Polymer I-21 10 Polymer I-22 10 PolymerI-23 10 Polymer I-24 10 Polymer I-25 10 Polymer I-26 10 Polymer I-27 10Polymer I-28 10 Polymer I-29 10 Polymer I-30 10 Polymer I-31 10 PolymerI-32 10 Polymer I-33 10 Polymer I-34 10 Polymer I-35 101-hydroxyethylidene-1,1- 10 bisphosphonic acid Carbon black (*1) — 20 2020 20 20 Pigment Blue 15:3 (*2) Pigment Red 122 (*3) — Pigment Yellow 74(*4) — Pure water — 30 30 30 30 30 Total — 100 100 100 100 100 (4) SolidContent Pigment Dispersion (%) I-16 I-17 I-18 I-19 Naphthalene 10sulfonic acid Na formalin condensate Polymer I-1 10 Polymer I-2 10Polymer I-3 10 Polymer I-4 10 Polymer I-5 10 Polymer I-6 10 Polymer I-710 Polymer I-8 10 Polymer I-9 10 Polymer I-10 10 Polymer I-11 10 PolymerI-12 10 Polymer I-13 10 Polymer I-14 10 50 50 50 Polymer I-15 10 50Polymer I-16 10 Polymer I-17 10 Polymer I-18 10 Polymer I-19 10 PolymerI-20 10 Polymer I-21 10 Polymer I-22 10 Polymer I-23 10 Polymer I-24 10Polymer I-25 10 Polymer I-26 10 Polymer I-27 10 Polymer I-28 10 PolymerI-29 10 Polymer I-30 10 Polymer I-31 10 Polymer I-32 10 Polymer I-33 10Polymer I-34 10 Polymer I-35 10 1-hydroxyethylidene-1,1- 10bisphosphonic acid Carbon black (*1) — 20 Pigment Blue 15:3 (*2) 20Pigment Red 122 (*3) — 20 Pigment Yellow 74 (*4) — 20 Pure water — 30 3030 30 Total — 100 100 100 100 (5) Solid Content Pigment Dispersion (%)I-20 I-21 I-22 I-23 I-24 Naphthalene 10 sulfonic acid Na formalincondensate Polymer I-1 10 Polymer I-2 10 Polymer I-3 10 Polymer I-4 10Polymer I-5 10 Polymer I-6 10 Polymer I-7 10 Polymer I-8 10 Polymer I-910 Polymer I-10 10 Polymer I-11 10 Polymer I-12 10 Polymer I-13 10Polymer I-14 10 Polymer I-15 10 Polymer I-16 10 50 Polymer I-17 10 50Polymer I-18 10 50 Polymer I-19 10 50 Polymer I-20 10 50 Polymer I-21 10Polymer I-22 10 Polymer I-23 10 Polymer I-24 10 Polymer I-25 10 PolymerI-26 10 Polymer I-27 10 Polymer I-28 10 Polymer I-29 10 Polymer I-30 10Polymer I-31 10 Polymer I-32 10 Polymer I-33 10 Polymer I-34 10 PolymerI-35 10 1-hydroxyethylidene-1,1- 10 bisphosphonic acid Carbon black (*1)— 20 20 20 20 20 Pigment Blue 15:3 (*2) Pigment Red 122 (*3) — PigmentYellow 74 (*4) — Pure water — 30 30 30 30 30 Total — 100 100 100 100 100(6) Solid Content Pigment Dispersion (%) I-25 I-26 I-27 I-28 I-29Naphthalene 10 sulfonic acid Na formalin condensate Polymer I-1 10Polymer I-2 10 Polymer I-3 10 Polymer I-4 10 Polymer I-5 10 Polymer I-610 Polymer I-7 10 Polymer I-8 10 Polymer I-9 10 Polymer I-10 10 PolymerI-11 10 Polymer I-12 10 Polymer I-13 10 Polymer I-14 10 Polymer I-15 10Polymer I-16 10 Polymer I-17 10 Polymer I-18 10 Polymer I-19 10 PolymerI-20 10 Polymer I-21 10 50 Polymer I-22 10 50 Polymer I-23 10 50 PolymerI-24 10 50 Polymer I-25 10 50 Polymer I-26 10 Polymer I-27 10 PolymerI-28 10 Polymer I-29 10 Polymer I-30 10 Polymer I-31 10 Polymer I-32 10Polymer I-33 10 Polymer I-34 10 Polymer I-35 10 1-hydroxyethylidene-1,1-10 bisphosphonic acid Carbon black (*1) — 20 20 20 20 20 Pigment Blue15:3 (*2) Pigment Red 122 (*3) — Pigment Yellow 74 (*4) — Pure water —30 30 30 30 30 Total — 100 100 100 100 100 (7) Solid Content PigmentDispersion (%) I-30 I-31 I-32 I-33 I-34 Naphthalene 10 sulfonic acid Naformalin condensate Polymer I-1 10 Polymer I-2 10 Polymer I-3 10 PolymerI-4 10 Polymer I-5 10 Polymer I-6 10 Polymer I-7 10 Polymer I-8 10Polymer I-9 10 Polymer I-10 10 Polymer I-11 10 Polymer I-12 10 PolymerI-13 10 Polymer I-14 10 Polymer I-15 10 Polymer I-16 10 Polymer I-17 10Polymer I-18 10 Polymer I-19 10 Polymer I-20 10 Polymer I-21 10 PolymerI-22 10 Polymer I-23 10 Polymer I-24 10 Polymer I-25 10 Polymer I-26 1050 Polymer I-27 10 50 Polymer I-28 10 50 Polymer I-29 10 50 Polymer I-3010 50 Polymer I-31 10 Polymer I-32 10 Polymer I-33 10 Polymer I-34 10Polymer I-35 10 1-hydroxyethylidene-1,1- 10 bisphosphonic acid Carbonblack (*1) — 20 20 20 20 20 Pigment Blue 15:3 (*2) Pigment Red 122 (*3)— Pigment Yellow 74 (*4) — Pure water — 30 30 30 30 30 Total — 100 100100 100 100 (8) Solid Content Pigment Dispersion (%) I-35 I-36 I-37 I-38Naphthalene 10 sulfonic acid Na formalin condensate Polymer I-1 10Polymer I-2 10 Polymer I-3 10 Polymer I-4 10 Polymer I-5 10 Polymer I-610 Polymer I-7 10 Polymer I-8 10 Polymer I-9 10 Polymer I-10 10 PolymerI-11 10 Polymer I-12 10 Polymer I-13 10 Polymer I-14 10 Polymer I-15 10Polymer I-16 10 Polymer I-17 10 Polymer I-18 10 Polymer I-19 10 PolymerI-20 10 Polymer I-21 10 Polymer I-22 10 Polymer I-23 10 Polymer I-24 10Polymer I-25 10 Polymer I-26 10 Polymer I-27 10 Polymer I-28 10 PolymerI-29 10 Polymer I-30 10 Polymer I-31 10 50 Polymer I-32 10 50 PolymerI-33 10 50 Polymer I-34 10 50 Polymer I-35 10 1-hydroxyethylidene-1,1-10 bisphosphonic acid Carbon black (*1) — 20 20 20 20 Pigment Blue 15:3(*2) Pigment Red 122 (*3) — Pigment Yellow 74 (*4) — Pure water — 30 3030 30 Total — 100 100 100 100 (9) Solid Content Pigment Dispersion (%)I-39 I-40 Naphthalene 10 sulfonic acid Na formalin condensate PolymerI-1 10 Polymer I-2 10 Polymer I-3 10 Polymer I-4 10 Polymer I-5 10Polymer I-6 10 Polymer I-7 10 Polymer I-8 10 Polymer I-9 10 Polymer I-1010 Polymer I-11 10 Polymer I-12 10 Polymer I-13 10 Polymer I-14 10Polymer I-15 10 Polymer I-16 10 Polymer I-17 10 Polymer I-18 10 PolymerI-19 10 Polymer I-20 10 Polymer I-21 10 Polymer I-22 10 Polymer I-23 10Polymer I-24 10 Polymer I-25 10 Polymer I-26 10 Polymer I-27 10 PolymerI-28 10 Polymer I-29 10 Polymer I-30 10 Polymer I-31 10 Polymer I-32 10Polymer I-33 10 Polymer I-34 10 Polymer I-35 10 501-hydroxyethylidene-1,1- 10 50 bisphosphonic acid Carbon black (*1) — 2020 Pigment Blue 15:3 (*2) Pigment Red 122 (*3) — Pigment Yellow 74 (*4)— Pure water — 30 30 Total — 100 100 (*1) = NIPEX 160 (*2) = CHROMOFINEBLUE A-220J from Dainichiseika Color & Chemicals Mfg. Co., Ltd. (*3) =Toner Magenta E-0002 from Clariant (*4) = FAST YELLOW 531 fromDainichiseika Color & Chemicals Mfg. Co., Ltd.

Preparation of Ink for Inkjet Recording Example I-1

The following materials were mixed, stirred for 1.5 hrs and filteredwith a membrane filter having an aperture of 1.2 nm to prepare an ink.

Pigment Dispersion 1 40.0 (including a solid content of pigment in anamount of 20% by weight) 1,3-butanediol (hydrosoluble solvent) 20.0Glycerin (hydrosoluble solvent) 10.0 2-ethyl-1,3-hexanediol(hydrosoluble solvent) 1.0 2,2,4-trimethyl-1,3-pentadiol (hydrosolublesolvent) 1.0 Fluorine surfactant 2.0 (Zonyl FS-300 from DuPont includinga solid content in an amount of 40% by weight) Aqueous solution ofpolymer I-14 20.0 (including a solid content in an amount of 10% byweight) Distilled water 6.0

Example I-2

The procedure for preparation of the ink in Example I-1 was repeatedexcept for replacing the pigment dispersion I-1 with the pigmentdispersion I-2 (Bk dispersion including polymer I-1) without the aqueoussolution of polymer I-14 and using 26.0 parts of distilled water insteadof 6.0 parts thereof to prepare an ink.

Example I-3

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-3 (Bk dispersion including polymer I-2).

Example I-4

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-4 (Bk dispersion including polymer I-3).

Example I-5

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-5 (Bk dispersion including polymer I-4).

Example I-6

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-6 (Bk dispersion including polymer I-5).

Example I-7

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-7 (Bk dispersion including polymer I-6).

Example I-8

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-8 (Bk dispersion including polymer I-7).

Example I-9

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-9 (Bk dispersion including polymer I-8).

Example I-10

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-10 (Bk dispersion including polymer I-9).

Example I-11

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-11 (Bk dispersion including polymer I-10).

Example I-12

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-12 (Bk dispersion including polymer I-11).

Example I-13

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-13 (Bk dispersion including polymer I-12).

Example I-14

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-14 (Bk dispersion including polymer I-13).

Example I-15

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-15 (Bk dispersion including polymer I-14).

Example I-16

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-16 (Cy dispersion including polymer I-14).

Example I-17

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-17 (Ma dispersion including polymer I-14).

Example I-18

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-18 (Ye dispersion including polymer I-14).

Example I-19

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-19 (Bk dispersion including polymer I-15).

Example I-20

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-20 (Bk dispersion including polymer I-16).

Example I-21

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-21 (Bk dispersion including polymer I-17).

Example I-22

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-22 (Bk dispersion including polymer I-18).

Example I-23

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-23 (Bk dispersion including polymer I-19) and using 26.0parts of distilled water instead of 6.0 parts thereof to prepare an ink.

Example I-24

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-24 (Bk dispersion including polymer I-20).

Example I-25

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-25 (Bk dispersion including polymer I-21).

Example I-26

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-26 (Bk dispersion including polymer I-22).

Example I-27

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-27 (Bk dispersion including polymer I-23).

Example I-28

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-28 (Bk dispersion including polymer I-24).

Example I-29

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-29 (Bk dispersion including polymer I-25).

Example I-30

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-30 (Bk dispersion including polymer I-26).

Example I-31

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-31 (Bk dispersion including polymer I-27).

Example I-32

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-32 (Bk dispersion including polymer I-28).

Example I-33

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-33 (Bk dispersion including polymer I-29).

Example I-34

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-34 (Bk dispersion including polymer I-30).

Example I-35

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-35 (Bk dispersion including polymer I-31).

Example I-36

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-36 (Bk dispersion including polymer I-32).

Example I-37

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-37 (Bk dispersion including polymer I-33).

Comparative Example I-1

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-38 (Bk dispersion including polymer I-34).

Comparative Example I-2

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-39 (Bk dispersion including polymer I-35).

Comparative Example I-3

The procedure for preparation of the ink in Example I-2 was repeatedexcept for replacing the pigment dispersion I-2 with the pigmentdispersion I-40 (Bk dispersion including1-hydroxyethylidene-1,1-bisphosphonic acid salt).

These formulations are summarized in Table I-3.

Bk represents black, Cy represents cyan, Ma represents magenta and Yerepresents yellow therein.

TABLE I-3 (1) Example Material I-1 I-2 I-3 I-4 I-5 Pigment Naphthalene40 dispersion I-1 sulfonic acid Na Pigment Bk dispersion 40 dispersionI-2 including polymer I-1 Pigment Bk dispersion 40 dispersion I-3including polymer I-2 Pigment Bk dispersion 40 dispersion I-4 includingpolymer I-3 Pigment Bk dispersion 40 dispersion I-5 including polymerI-4 Pigment Bk dispersion dispersion I-6 including polymer I-5 PigmentBk dispersion dispersion I-7 including polymer I-6 Pigment Bk dispersiondispersion I-8 including polymer I-7 Pigment Bk dispersion dispersionI-9 including polymer I-8 Pigment Bk dispersion dispersion I-10including polymer I-9 Pigment Bk dispersion dispersion I-11 includingpolymer I-10 Pigment Bk dispersion dispersion I-12 including polymerI-11 Pigment Bk dispersion dispersion I-13 including polymer I-12Pigment Bk dispersion dispersion I-14 including polymer I-13 Pigment Bkdispersion dispersion I-15 including polymer I-14 Pigment Cy dispersiondispersion I-16 including polymer I-14 Pigment Ma dispersion dispersionI-17 including polymer I-14 Pigment Ye dispersion dispersion I-18including polymer I-14 Pigment Bk dispersion dispersion I-19 includingpolymer I-15 Pigment Bk dispersion dispersion I-20 including polymerI-16 Pigment Bk dispersion dispersion I-21 including polymer I-17Pigment Bk dispersion dispersion I-22 including polymer I-18 Pigment Bkdispersion dispersion I-23 including polymer I-19 Pigment Bk dispersiondispersion I-24 including polymer I-20 Pigment Bk dispersion dispersionI-25 including polymer I-21 Pigment Bk dispersion dispersion I-26including polymer I-22 Pigment Bk dispersion dispersion I-27 includingpolymer I-23 Pigment Bk dispersion dispersion I-28 including polymerI-24 Pigment Bk dispersion dispersion I-29 including polymer I-25Pigment Bk dispersion dispersion I-30 including polymer I-26 Pigment Bkdispersion dispersion I-31 including polymer I-27 Pigment Bk dispersiondispersion I-32 including polymer I-28 Pigment Bk dispersion dispersionI-33 including polymer I-29 Pigment Bk dispersion dispersion I-34including polymer I-30 Pigment Bk dispersion dispersion I-35 includingpolymer I-31 Pigment Bk dispersion dispersion I-36 including polymerI-32 Pigment Bk dispersion dispersion I-37 including polymer I-33Pigment Bk dispersion dispersion I-38 including polymer I-34 Pigment Bkdispersion dispersion I-39 including polymer I-35 Pigment Bk dispersiondispersion I-40 including 1- hydroxyethylidene- 1,1-bisphosphonic acidsalt Aqueous solution of polymer 20 I-14 including a solid content in anamount of 10% by weight Glycerin 10 10 10 10 10 1,3- 20 20 20 20 20butanediol 2-ethyl-1,3- 1 1 1 1 1 hexanediol 2,2,4- 1 1 1 1 1trimethyl-1,3- pentadiol Surfactant 2 2 2 2 2 (Zonyl FS-300) Distilledwater 6 26 26 26 26 Total 100 100 100 100 100 (2) Example Material I-6I-7 I-8 I-9 I-10 Pigment Naphthalene dispersion I-1 sulfonic acid NaPigment Bk dispersion dispersion I-2 including polymer I-1 Pigment Bkdispersion dispersion I-3 including polymer I-2 Pigment Bk dispersiondispersion I-4 including polymer I-3 Pigment Bk dispersion dispersionI-5 including polymer I-4 Pigment Bk dispersion 40 dispersion I-6including polymer I-5 Pigment Bk dispersion 40 dispersion I-7 includingpolymer I-6 Pigment Bk dispersion 40 dispersion I-8 including polymerI-7 Pigment Bk dispersion 40 dispersion I-9 including polymer I-8Pigment Bk dispersion 40 dispersion I-10 including polymer I-9 PigmentBk dispersion dispersion I-11 including polymer I-10 Pigment Bkdispersion dispersion I-12 including polymer I-11 Pigment Bk dispersiondispersion I-13 including polymer I-12 Pigment Bk dispersion dispersionI-14 including polymer I-13 Pigment Bk dispersion dispersion I-15including polymer I-14 Pigment Cy dispersion dispersion I-16 includingpolymer I-14 Pigment Ma dispersion dispersion I-17 including polymerI-14 Pigment Ye dispersion dispersion I-18 including polymer I-14Pigment Bk dispersion dispersion I-19 including polymer I-15 Pigment Bkdispersion dispersion I-20 including polymer I-16 Pigment Bk dispersiondispersion I-21 including polymer I-17 Pigment Bk dispersion dispersionI-22 including polymer I-18 Pigment Bk dispersion dispersion I-23including polymer I-19 Pigment Bk dispersion dispersion I-24 includingpolymer I-20 Pigment Bk dispersion dispersion I-25 including polymerI-21 Pigment Bk dispersion dispersion I-26 including polymer I-22Pigment Bk dispersion dispersion I-27 including polymer I-23 Pigment Bkdispersion dispersion I-28 including polymer I-24 Pigment Bk dispersiondispersion I-29 including polymer I-25 Pigment Bk dispersion dispersionI-30 including polymer I-26 Pigment Bk dispersion dispersion I-31including polymer I-27 Pigment Bk dispersion dispersion I-32 includingpolymer I-28 Pigment Bk dispersion dispersion I-33 including polymerI-29 Pigment Bk dispersion dispersion I-34 including polymer I-30Pigment Bk dispersion dispersion I-35 including polymer I-31 Pigment Bkdispersion dispersion I-36 including polymer I-32 Pigment Bk dispersiondispersion I-37 including polymer I-33 Pigment Bk dispersion dispersionI-38 including polymer I-34 Pigment Bk dispersion dispersion I-39including polymer I-35 Pigment Bk dispersion dispersion I-40 including1- hydroxyethylidene- 1,1-bisphosphonic acid salt Aqueous solution ofpolymer I-14 including a solid content in an amount of 10% by weightGlycerin 10 10 10 10 10 1,3- 20 20 20 20 20 butanediol 2-ethyl-1,3- 1 11 1 1 hexanediol 2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 22 2 2 2 (Zonyl FS-300) Distilled water 26 26 26 26 26 Total 100 100 100100 100 (3) Example Material I-11 I-12 I-13 I-14 I-15 PigmentNaphthalene dispersion I-1 sulfonic acid Na Pigment Bk dispersiondispersion I-2 including polymer I-1 Pigment Bk dispersion dispersionI-3 including polymer I-2 Pigment Bk dispersion dispersion I-4 includingpolymer I-3 Pigment Bk dispersion dispersion I-5 including polymer I-4Pigment Bk dispersion dispersion I-6 including polymer I-5 Pigment Bkdispersion dispersion I-7 including polymer I-6 Pigment Bk dispersiondispersion I-8 including polymer I-7 Pigment Bk dispersion dispersionI-9 including polymer I-8 Pigment Bk dispersion dispersion I-10including polymer I-9 Pigment Bk dispersion 40 dispersion I-11 includingpolymer I-10 Pigment Bk dispersion 40 dispersion I-12 including polymerI-11 Pigment Bk dispersion 40 dispersion I-13 including polymer I-12Pigment Bk dispersion 40 dispersion I-14 including polymer I-13 PigmentBk dispersion 40 dispersion I-15 including polymer I-14 Pigment Cydispersion dispersion I-16 including polymer I-14 Pigment Ma dispersiondispersion I-17 including polymer I-14 Pigment Ye dispersion dispersionI-18 including polymer I-14 Pigment Bk dispersion dispersion I-19including polymer I-15 Pigment Bk dispersion dispersion I-20 includingpolymer I-16 Pigment Bk dispersion dispersion I-21 including polymerI-17 Pigment Bk dispersion dispersion I-22 including polymer I-18Pigment Bk dispersion dispersion I-23 including polymer I-19 Pigment Bkdispersion dispersion I-24 including polymer I-20 Pigment Bk dispersiondispersion I-25 including polymer I-21 Pigment Bk dispersion dispersionI-26 including polymer I-22 Pigment Bk dispersion dispersion I-27including polymer I-23 Pigment Bk dispersion dispersion I-28 includingpolymer I-24 Pigment Bk dispersion dispersion I-29 including polymerI-25 Pigment Bk dispersion dispersion I-30 including polymer I-26Pigment Bk dispersion dispersion I-31 including polymer I-27 Pigment Bkdispersion dispersion I-32 including polymer I-28 Pigment Bk dispersiondispersion I-33 including polymer I-29 Pigment Bk dispersion dispersionI-34 including polymer I-30 Pigment Bk dispersion dispersion I-35including polymer I-31 Pigment Bk dispersion dispersion I-36 includingpolymer I-32 Pigment Bk dispersion dispersion I-37 including polymerI-33 Pigment Bk dispersion dispersion I-38 including polymer I-34Pigment Bk dispersion dispersion I-39 including polymer I-35 Pigment Bkdispersion dispersion I-40 including 1- hydroxyethylidene-1,1-bisphosphonic acid salt Aqueous solution of polymer I-14 including asolid content in an amount of 10% by weight Glycerin 10 10 10 10 10 1,3-20 20 20 20 20 butanediol 2-ethyl-1,3- 1 1 1 1 1 hexanediol 2,2,4- 1 1 11 1 trimethyl-1,3- pentadiol Surfactant 2 2 2 2 2 (Zonyl FS-300)Distilled water 26 26 26 26 26 Total 100 100 100 100 100 (4) ExampleMaterial I-16 I-17 I-18 I-19 I-20 Pigment Naphthalene dispersion I-1sulfonic acid Na Pigment Bk dispersion dispersion I-2 including polymerI-1 Pigment Bk dispersion dispersion I-3 including polymer I-2 PigmentBk dispersion dispersion I-4 including polymer I-3 Pigment Bk dispersiondispersion I-5 including polymer I-4 Pigment Bk dispersion dispersionI-6 including polymer I-5 Pigment Bk dispersion dispersion I-7 includingpolymer I-6 Pigment Bk dispersion dispersion I-8 including polymer I-7Pigment Bk dispersion dispersion I-9 including polymer I-8 Pigment Bkdispersion 40 dispersion I-10 including polymer I-9 Pigment Bkdispersion dispersion I-11 including polymer I-10 Pigment Bk dispersiondispersion I-12 including polymer I-11 Pigment Bk dispersion dispersionI-13 including polymer I-12 Pigment Bk dispersion dispersion I-14including polymer I-13 Pigment Bk dispersion dispersion I-15 includingpolymer I-14 Pigment Cy dispersion 40 dispersion I-16 including polymerI-14 Pigment Ma dispersion 40 dispersion I-17 including polymer I-14Pigment Ye dispersion 40 dispersion I-18 including polymer I-14 PigmentBk dispersion 40 dispersion I-19 including polymer I-15 Pigment Bkdispersion 40 dispersion I-20 including polymer I-16 Pigment Bkdispersion dispersion I-21 including polymer I-17 Pigment Bk dispersiondispersion I-22 including polymer I-18 Pigment Bk dispersion dispersionI-23 including polymer I-19 Pigment Bk dispersion dispersion I-24including polymer I-20 Pigment Bk dispersion dispersion I-25 includingpolymer I-21 Pigment Bk dispersion dispersion I-26 including polymerI-22 Pigment Bk dispersion dispersion I-27 including polymer I-23Pigment Bk dispersion dispersion I-28 including polymer I-24 Pigment Bkdispersion dispersion I-29 including polymer I-25 Pigment Bk dispersiondispersion I-30 including polymer I-26 Pigment Bk dispersion dispersionI-31 including polymer I-27 Pigment Bk dispersion dispersion I-32including polymer I-28 Pigment Bk dispersion dispersion I-33 includingpolymer I-29 Pigment Bk dispersion dispersion I-34 including polymerI-30 Pigment Bk dispersion dispersion I-35 including polymer I-31Pigment Bk dispersion dispersion I-36 including polymer I-32 Pigment Bkdispersion dispersion I-37 including polymer I-33 Pigment Bk dispersiondispersion I-38 including polymer I-34 Pigment Bk dispersion dispersionI-39 including polymer I-35 Pigment Bk dispersion dispersion I-40including 1- hydroxyethylidene- 1,1-bisphosphonic acid salt Aqueoussolution of polymer I-14 including a solid content in an amount of 10%by weight Glycerin 10 10 10 10 10 1,3- 20 20 20 20 20 butanediol2-ethyl-1,3- 1 1 1 1 1 hexanediol 2,2,4- 1 1 1 1 1 trimethyl-1,3-pentadiol Surfactant 2 2 2 2 2 (Zonyl FS-300) Distilled water 26 26 2626 26 Total 100 100 100 100 100 (5) Example Material I-21 I-22 I-23 I-24I-25 Pigment Naphthalene dispersion I-1 sulfonic acid Na Pigment Bkdispersion dispersion I-2 including polymer I-1 Pigment Bk dispersiondispersion I-3 including polymer I-2 Pigment Bk dispersion dispersionI-4 including polymer I-3 Pigment Bk dispersion dispersion I-5 includingpolymer I-4 Pigment Bk dispersion dispersion I-6 including polymer I-5Pigment Bk dispersion dispersion I-7 including polymer I-6 Pigment Bkdispersion dispersion I-8 including polymer I-7 Pigment Bk dispersiondispersion I-9 including polymer I-8 Pigment Bk dispersion dispersionI-10 including polymer I-9 Pigment Bk dispersion dispersion I-11including polymer I-10 Pigment Bk dispersion dispersion I-12 includingpolymer I-11 Pigment Bk dispersion dispersion I-13 including polymerI-12 Pigment Bk dispersion dispersion I-14 including polymer I-13Pigment Bk dispersion dispersion I-15 including polymer I-14 Pigment Cydispersion dispersion I-16 including polymer I-14 Pigment Ma dispersiondispersion I-17 including polymer I-14 Pigment Ye dispersion dispersionI-18 including polymer I-14 Pigment Bk dispersion dispersion I-19including polymer I-15 Pigment Bk dispersion dispersion I-20 includingpolymer I-16 Pigment Bk dispersion 40 dispersion I-21 including polymerI-17 Pigment Bk dispersion 40 dispersion I-22 including polymer I-18Pigment Bk dispersion 40 dispersion I-23 including polymer I-19 PigmentBk dispersion 40 dispersion I-24 including polymer I-20 Pigment Bkdispersion 40 dispersion I-25 including polymer I-21 Pigment Bkdispersion dispersion I-26 including polymer I-22 Pigment Bk dispersiondispersion I-27 including polymer I-23 Pigment Bk dispersion dispersionI-28 including polymer I-24 Pigment Bk dispersion dispersion I-29including polymer I-25 Pigment Bk dispersion dispersion I-30 includingpolymer I-26 Pigment Bk dispersion dispersion I-31 including polymerI-27 Pigment Bk dispersion dispersion I-32 including polymer I-28Pigment Bk dispersion dispersion I-33 including polymer I-29 Pigment Bkdispersion dispersion I-34 including polymer I-30 Pigment Bk dispersiondispersion I-35 including polymer I-31 Pigment Bk dispersion dispersionI-36 including polymer I-32 Pigment Bk dispersion dispersion I-37including polymer I-33 Pigment Bk dispersion dispersion I-38 includingpolymer I-34 Pigment Bk dispersion dispersion I-39 including polymerI-35 Pigment Bk dispersion dispersion I-40 including 1-hydroxyethylidene- 1,1-bisphosphonic acid salt Aqueous solution ofpolymer I-14 including a solid content in an amount of 10% by weightGlycerin 10 10 10 10 10 1,3- 20 20 20 20 20 butanediol 2-ethyl-1,3- 1 11 1 1 hexanediol 2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 22 2 2 2 (Zonyl FS-300) Distilled water 26 26 26 26 26 Total 100 100 100100 100 (6) Example Material I-26 I-27 I-28 I-29 I-30 PigmentNaphthalene dispersion I-1 sulfonic acid Na Pigment Bk dispersiondispersion I-2 including polymer I-1 Pigment Bk dispersion dispersionI-3 including polymer I-2 Pigment Bk dispersion dispersion I-4 includingpolymer I-3 Pigment Bk dispersion dispersion I-5 including polymer I-4Pigment Bk dispersion dispersion I-6 including polymer I-5 Pigment Bkdispersion dispersion I-7 including polymer I-6 Pigment Bk dispersiondispersion I-8 including polymer I-7 Pigment Bk dispersion dispersionI-9 including polymer I-8 Pigment Bk dispersion dispersion I-10including polymer I-9 Pigment Bk dispersion dispersion I-11 includingpolymer I-10 Pigment Bk dispersion dispersion I-12 including polymerI-11 Pigment Bk dispersion dispersion I-13 including polymer I-12Pigment Bk dispersion dispersion I-14 including polymer I-13 Pigment Bkdispersion dispersion I-15 including polymer I-14 Pigment Cy dispersiondispersion I-16 including polymer I-14 Pigment Ma dispersion dispersionI-17 including polymer I-14 Pigment Ye dispersion dispersion I-18including polymer I-14 Pigment Bk dispersion dispersion I-19 includingpolymer I-15 Pigment Bk dispersion dispersion I-20 including polymerI-16 Pigment Bk dispersion dispersion I-21 including polymer I-17Pigment Bk dispersion dispersion I-22 including polymer I-18 Pigment Bkdispersion dispersion I-23 including polymer I-19 Pigment Bk dispersiondispersion I-24 including polymer I-20 Pigment Bk dispersion dispersionI-25 including polymer I-21 Pigment Bk dispersion 40 dispersion I-26including polymer I-22 Pigment Bk dispersion 40 dispersion I-27including polymer I-23 Pigment Bk dispersion 40 dispersion I-28including polymer I-24 Pigment Bk dispersion 40 dispersion I-29including polymer I-25 Pigment Bk dispersion 40 dispersion I-30including polymer I-26 Pigment Bk dispersion dispersion I-31 includingpolymer I-27 Pigment Bk dispersion dispersion I-32 including polymerI-28 Pigment Bk dispersion dispersion I-33 including polymer I-29Pigment Bk dispersion dispersion I-34 including polymer I-30 Pigment Bkdispersion dispersion I-35 including polymer I-31 Pigment Bk dispersiondispersion I-36 including polymer I-32 Pigment Bk dispersion dispersionI-37 including polymer I-33 Pigment Bk dispersion dispersion I-38including polymer I-34 Pigment Bk dispersion dispersion I-39 includingpolymer I-35 Pigment Bk dispersion dispersion I-40 including 1-hydroxyethylidene- 1,1-bisphosphonic acid salt Aqueous solution ofpolymer I-14 including a solid content in an amount of 10% by weightGlycerin 10 10 10 10 10 1,3- 20 20 20 20 20 butanediol 2-ethyl-1,3- 1 11 1 1 hexanediol 2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 22 2 2 2 (Zonyl FS-300) Distilled water 26 26 26 26 26 Total 100 100 100100 100 (7) Example Material I-31 I-32 I-33 I-34 I-35 PigmentNaphthalene dispersion I-1 sulfonic acid Na Pigment Bk dispersiondispersion I-2 including polymer I-1 Pigment Bk dispersion dispersionI-3 including polymer I-2 Pigment Bk dispersion dispersion I-4 includingpolymer I-3 Pigment Bk dispersion dispersion I-5 including polymer I-4Pigment Bk dispersion dispersion I-6 including polymer I-5 Pigment Bkdispersion dispersion I-7 including polymer I-6 Pigment Bk dispersiondispersion I-8 including polymer I-7 Pigment Bk dispersion dispersionI-9 including polymer I-8 Pigment Bk dispersion dispersion I-10including polymer I-9 Pigment Bk dispersion dispersion I-11 includingpolymer I-10 Pigment Bk dispersion dispersion I-12 including polymerI-11 Pigment Bk dispersion dispersion I-13 including polymer I-12Pigment Bk dispersion dispersion I-14 including polymer I-13 Pigment Bkdispersion dispersion I-15 including polymer I-14 Pigment Cy dispersiondispersion I-16 including polymer I-14 Pigment Ma dispersion dispersionI-17 including polymer I-14 Pigment Ye dispersion dispersion I-18including polymer I-14 Pigment Bk dispersion dispersion I-19 includingpolymer I-15 Pigment Bk dispersion dispersion I-20 including polymerI-16 Pigment Bk dispersion dispersion I-21 including polymer I-17Pigment Bk dispersion dispersion I-22 including polymer I-18 Pigment Bkdispersion dispersion I-23 including polymer I-19 Pigment Bk dispersiondispersion I-24 including polymer I-20 Pigment Bk dispersion dispersionI-25 including polymer I-21 Pigment Bk dispersion dispersion I-26including polymer I-22 Pigment Bk dispersion dispersion I-27 includingpolymer I-23 Pigment Bk dispersion dispersion I-28 including polymerI-24 Pigment Bk dispersion dispersion I-29 including polymer I-25Pigment Bk dispersion dispersion I-30 including polymer I-26 Pigment Bkdispersion 40 dispersion I-31 including polymer I-27 Pigment Bkdispersion 40 dispersion I-32 including polymer I-28 Pigment Bkdispersion 40 dispersion I-33 including polymer I-29 Pigment Bkdispersion 40 dispersion I-34 including polymer I-30 Pigment Bkdispersion 40 dispersion I-35 including polymer I-31 Pigment Bkdispersion dispersion I-36 including polymer I-32 Pigment Bk dispersiondispersion I-37 including polymer I-33 Pigment Bk dispersion dispersionI-38 including polymer I-34 Pigment Bk dispersion dispersion I-39including polymer I-35 Pigment Bk dispersion dispersion I-40 including1- hydroxyethylidene- 1,1-bisphosphonic acid salt Aqueous solution ofpolymer I-14 including a solid content in an amount of 10% by weightGlycerin 10 10 10 10 10 1,3- 20 20 20 20 20 butanediol 2-ethyl-1,3- 1 11 1 1 hexanediol 2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 22 2 2 2 (Zonyl FS-300) Distilled water 2 26 26 26 26 Total 100 100 100100 100 (8) Example Com. Example Material I-36 I-37 I-1 I-2 I-3 PigmentNaphthalene dispersion I-1 sulfonic acid Na Pigment Bk dispersiondispersion I-2 including polymer I-1 Pigment Bk dispersion dispersionI-3 including polymer I-2 Pigment Bk dispersion dispersion I-4 includingpolymer I-3 Pigment Bk dispersion dispersion I-5 including polymer I-4Pigment Bk dispersion dispersion I-6 including polymer I-5 Pigment Bkdispersion dispersion I-7 including polymer I-6 Pigment Bk dispersiondispersion I-8 including polymer I-7 Pigment Bk dispersion dispersionI-9 including polymer I-8 Pigment Bk dispersion dispersion I-10including polymer I-9 Pigment Bk dispersion dispersion I-11 includingpolymer I-10 Pigment Bk dispersion dispersion I-12 including polymerI-11 Pigment Bk dispersion dispersion I-13 including polymer I-12Pigment Bk dispersion dispersion I-14 including polymer I-13 Pigment Bkdispersion dispersion I-15 including polymer I-14 Pigment Cy dispersiondispersion I-16 including polymer I-14 Pigment Ma dispersion dispersionI-17 including polymer I-14 Pigment Ye dispersion dispersion I-18including polymer I-14 Pigment Bk dispersion dispersion I-19 includingpolymer I-15 Pigment Bk dispersion dispersion I-20 including polymerI-16 Pigment Bk dispersion dispersion I-21 including polymer I-17Pigment Bk dispersion dispersion I-22 including polymer I-18 Pigment Bkdispersion dispersion I-23 including polymer I-19 Pigment Bk dispersiondispersion I-24 including polymer I-20 Pigment Bk dispersion dispersionI-25 including polymer I-21 Pigment Bk dispersion dispersion I-26including polymer I-22 Pigment Bk dispersion dispersion I-27 includingpolymer I-23 Pigment Bk dispersion dispersion I-28 including polymerI-24 Pigment Bk dispersion dispersion I-29 including polymer I-25Pigment Bk dispersion dispersion I-30 including polymer I-26 Pigment Bkdispersion dispersion I-31 including polymer I-27 Pigment Bk dispersiondispersion I-32 including polymer I-28 Pigment Bk dispersion dispersionI-33 including polymer I-29 Pigment Bk dispersion dispersion I-34including polymer I-30 Pigment Bk dispersion dispersion I-35 includingpolymer I-31 Pigment Bk dispersion 40 dispersion I-36 including polymerI-32 Pigment Bk dispersion 40 dispersion I-37 including polymer I-33Pigment Bk dispersion 40 dispersion I-38 including polymer I-34 PigmentBk dispersion 40 dispersion I-39 including polymer I-35 Pigment Bkdispersion 40 dispersion I-40 including 1- hydroxyethylidene-1,1-bisphosphonic acid salt Aqueous solution of polymer I-14 including asolid content in an amount of 10% by weight Glycerin 10 10 10 10 10 1,3-20 20 20 20 20 butanediol 2-ethyl-1,3- 1 1 1 1 1 hexanediol 2,2,4- 1 1 11 1 trimethyl-1,3- pentadiol Surfactant 2 2 2 2 2 (Zonyl FS-300)Distilled water 2 26 26 26 26 Total 100 100 100 100 100

The inks for inkjet recording of Examples I-1 to I-37 and ComparativeExamples I-1 to I-3 were evaluated by the following methods. The resultsare shown in Table I-4.

<Image Density (ID)>

In an environment of 23° C. and 50 RH, the ink was filled in an inkjetprinter IPSiO GX5000 from Ricoh Company, Ltd. After a chart on whichgeneral marks “▪” of JIS X 0208 (1997), 2223 having 64 points aredescribed by Microsoft Word 2003 was printed on a plain paper 1 (XEROX4200 from XEROX, Inc.) and a plain paper 2 (My Paper from Ricoh Company,Ltd.), the image density of “▪” was evaluated using X-Rite938 fromX-Rite, Inc. Then, the printing mode was “plain paper-fast” mode by adriver of the printer without color calibration.

Image density was evaluated under the following standard.

(Black)

A: not less than 1.25

B: not less than 1.20 and less than 1.25

C: not less than 1.10 and less than 1.20

D: less than 1.10

E: Unprintable as pigment was gelated and undispersible

(Yellow)

A: not less than 0.80

B: not less than 0.75 and less than 0.80

C: not less than 0.70 and less than 0.75

D: less than 0.70

E: Unprintable as pigment was gelated and undispersible

(Magenta)

A: not less than 0.95

B: not less than 0.85 and less than 0.95

C: not less than 0.75 and less than 0.85

D: less than 0.75

E: Unprintable as pigment was gelated and undispersible

(Cyan)

A: not less than 1.05

B: not less than 0.95 and less than 1.05

C: not less than 0.85 and less than 0.95

D: less than 0.85

E: Unprintable as pigment was gelated and undispersible

<Storage Stability of Pigment Dispersion>

Each of the pigment dispersions was placed in a polyethylene containerand sealed.

The viscosity after stored at 60° C. for 1 week was measured to evaluateunder the following standard, compared with the initial viscosity.

Viscosity Variation(%)=(Viscosity after Stored/Viscosity beforeStored)×100

The viscosity was measured by a viscometer RE500L from TOKI SANGYO CO.,LTD. at 25° C., adjusting the rotational number at from 50 to 100 rpmaccording the viscosity.

A: Viscosity variation was not greater than ±5%

B: Viscosity variation was greater than ±5% and not greater than ±8%

C: Viscosity variation was greater than ±8% and not greater than ±10%

D: Viscosity variation was greater than ±10% and not greater than ±30%

E: Viscosity variation was greater than ±30% (Unevaluable as pigment wasgelated)

<Storage Stability of Ink>

Each of the inks was filled in an ink cartridge. The viscosity afterstored at 60° C. for 1 week was measured to evaluate under the followingstandard, compared with the initial viscosity.

Viscosity Variation(%)=(Viscosity after Stored/Viscosity beforeStored)×100

The viscosity was measured by a viscometer RE500L from TOKI SANGYO CO.,LTD. at 25° C., adjusting the rotational number at from 50 to 100 rpmaccording the viscosity.

A: Viscosity variation was not greater than ±5%

B: Viscosity variation was greater than ±5% and not greater than ±8%

C: Viscosity variation was greater than ±8% and not greater than ±10%

D: Viscosity variation was greater than ±10% and not greater than ±30%

E: Viscosity variation was greater than ±30% (Unevaluable as pigment wasgelated)

TABLE I-4 Evaluation Results Storage Stability Stor- ID ID of agePigment Plain Plain Pigment Stability Dispersion Paper 1 Paper 2Dispersion of Ink Example I-1 Pigment B B B B Dispersion I-1 Example I-2Pigment B B A B Dispersion I-2 Example I-3 Pigment B B A B DispersionI-3 Example I-4 Pigment A A A A Dispersion I-4 Example I-5 Pigment A A AA Dispersion I-5 Example I-6 Pigment A A A A Dispersion I-6 Example I-7Pigment A A A A Dispersion I-7 Example I-8 Pigment A A A A DispersionI-8 Example I-9 Pigment A A A A Dispersion I-9 Example I-10 Pigment A AA A Dispersion I-10 Example I-11 Pigment A A A A Dispersion I-11 ExampleI-12 Pigment B B A A Dispersion I-12 Example I-13 Pigment A B A ADispersion I-13 Example I-14 Pigment A A A A Dispersion I-14 ExampleI-15 Pigment A A A A Dispersion I-15 Example I-16 Pigment A A A ADispersion I-16 Example I-17 Pigment A A A A Dispersion I-17 ExampleI-18 Pigment A A A A Dispersion I-18 Example I-19 Pigment A A A ADispersion I-19 Example I-20 Pigment A A B A Dispersion I-20 ExampleI-21 Pigment A A B B Dispersion I-21 Example I-22 Pigment A A A ADispersion I-22 Example I-23 Pigment A A A A Dispersion I-23 ExampleI-24 Pigment A A A A Dispersion I-24 Example I-25 Pigment A A A ADispersion I-25 Example I-26 Pigment A A A A Dispersion I-26 ExampleI-27 Pigment A A A A Dispersion I-27 Example I-28 Pigment A A A ADispersion I-28 Example I-29 Pigment A A A A Dispersion I-29 ExampleI-30 Pigment A A A A Dispersion I-30 Example I-31 Pigment A A A ADispersion I-31 Example I-32 Pigment B B A A Dispersion I-32 ExampleI-33 Pigment A A A A Dispersion I-33 Example I-34 Pigment A A A ADispersion I-34 Example I-35 Pigment A A B B Dispersion I-35 ExampleI-36 Pigment A A A A Dispersion I-36 Example I-37 Pigment A A A ADispersion I-37 Comparative Pigment E C E E Example I-1 Dispersion I-38Comparative Pigment E C E E Example I-2 Dispersion I-39 ComparativePigment E E E E Example I-3 Dispersion I-40

Table I-4 shows the inks of Examples produce images having higher imagedensity than those produced by the inks of Comparative Examples even ontypical plain papers, and have good storage stability even whenincluding the hydrosoluble organic solvent in an amount greater than 20%by weight.

Synthesis of Monomer Monomer No. II-1:4-methacrylamide-1-hydroxybutane-1,1-diphosphonic acid di sodium salt

In a flask, 25 parts of alendronic acid from Tokyo Chemical IndustryCo., Ltd. were placed, and an aqueous solution including 17.1 parts ofsodium hydroxide from Kanto Chemical Co., Inc. and 200 parts ofion-exchanged water was placed therein to be completely dissolved whilestirred. Next, 13.32 parts of methacrylic acid chloride from TokyoChemical Industry Co., Ltd. were slowly dropped therein while cooled at5° C. After stirred for 30 min, 14.53 parts of concentrated hydrochloricacid from Wako Pure Chemical Industries, Ltd. were dropped therein whilecooled. The reacted liquid was extracted and washed for 3 times withmethylene chloride, and the remaining aqueous solution was dropped in800 parts of methanol and filtered to extract 35 parts of an object.

One point seven (1.7) parts of the object were dissolved in 176 parts ofion-exchanged water to prepare a solution, and the solution wassubjected to neutralization titration in 0.1 N of KOH methanol solutionwith thymolphthalein from Kanto Chemical Co., Inc. as an indicator todetermine an acid value. The acid value was 155 mg KOH/g. Compared withthe titration result of the alendronic acid, the acid value was the samewhen 2 OH groups were replaced with Na salts.

Monomer No. II-2: 4-methacrylamide-hydroxybutane-1,1-diphosphonic aciddi potassium salt

The procedure for preparation of the object in synthesis of Monomer No.II-1 was repeated except for replacing 17.1 parts of sodium hydroxidewith 24 parts of potassium hydroxide from Wako Pure Chemical Industries,Ltd. to prepare 40 parts of an object.

Monomer No. II-3: 4-acrylamide-1-hydroxybutane-1,1-diphosphonic acid disodium salt

The procedure for preparation of the object in synthesis of Monomer No.II-1 was repeated except for replacing 13.32 parts of methacrylic acidchloride with 11.53 parts of acrylic acid chloride from Tokyo ChemicalIndustry Co., Ltd. to prepare 33 parts of an object.

Monomer No. II-4: 4-acrylamide-1-hydroxybutane-1,1-diphosphonic aciddi(triethyl ammonium) salt

The procedure for preparation of the object in synthesis of Monomer No.II-1 was repeated except for replacing 13.32 parts of methacrylic acidchloride with 11.53 parts of acrylic acid chloride, and 17.1 parts ofsodium hydroxide with 43.3 parts of triethylamine from Kanto ChemicalCo., Inc. to prepare 44 parts of an object.

Monomer No. II-5: 4-methacrylamide-1-hydroxybutane 1,1-diphosphoic aciddi(tetraethylammonium) salt)

The procedure for preparation of the object in synthesis of Monomer No.1 was repeated except for replacing 17.1 parts of sodium hydroxide with179.8 parts of tetraethylammonium hydroxide (35% aqueous solution) fromKanto Chemical Co., Inc., and 200 parts of ion-exchanged water with 83.1parts thereof to prepare 55 parts of an object.

Monomer No. II-6: 4-methacrylamide-1-hydroxybutane 1,1-diphosphoic aciddi(tetrabutylammonium) salt)

The procedure for preparation of the object in synthesis of Monomer No.1 was repeated except for replacing 17.1 parts of sodium hydroxide with277.2 parts of tetraethylammonium hydroxide (40% aqueous solution) fromKanto Chemical Co., Inc., and 200 parts of ion-exchanged water with 33.7parts thereof to prepare 76 parts of an object.

Synthesis Example II-1 Copolymer (Polymer II-1) Including a Salt ofPhosphonic Acid Group

In a reaction container including a gas inlet tube, a thermometer and areflux condenser, in an argon atmosphere, 450 parts ofN-dimethylformamide (DMF) were placed and heated at 75° C. In thecontainer, 223 parts of aqueous solution including 30 parts of themonomer No. II-1 as the monomer having the formula (4) and 193 parts ofwater, 212 parts of a DMF solution including 27 parts ofcyclohexylmethacrylate from Tokyo Chemical Industry Co., Ltd. as themonomer having the formula (5), 3 parts ofN-[3-(dimethylamino)propyl]acrylamide (DMAPAA) from Tokyo ChemicalIndustry Co., Ltd. as the monomer having the formula (6a) and 182 partsof DMF, and 187.4 parts of a DMF solution including 5.4 parts of2,2′-azobisisobutylonitrile (AIBN) and 182 parts of DMF were added in 12batches every 30 min. After these were all added therein, the mixturewas further stirred for 4 hrs at 75° C., cooled and the polymerizationwas completed.

The extract was filtered, washed with hexane, and vacuum-dried at 50° C.to obtain 62 parts of a copolymer (polymer II-1).

One (1) part of the resin (copolymer) was dissolved in 100 parts ofion-exchanged water to prepare a solution, and the solution wassubjected to neutralization titration in 0.1 N of KOH methanol solutionwith thymolphthalein as an indicator to determine an acid value. Theacid value was 77 mg KOH/g. This was almost same as 77 mg KOH/gdetermined from the acid value of the monomer No. II-1 assumingcopolymerization had been made in proportion to the place-in quantity.

Based on the acid value, the copolymer was neutralized with sodiumhydroxide to prepare an aqueous solution including 10% by weight of theresin. The solution had a viscosity of 1.7 mPa·s at 25° C.

The aqueous solution including 10% by weight of the resin was used forpreparing a pigment dispersion. From the titration result of thealendronic acid (monomer material), 3 OH groups out of 4 of thephosphonic acid were proved to be neutralized by sodium ion. The resultsare shown in Table II-1.

Synthesis Example II-2 Synthesis of Polymer II-2

The procedure for preparation of the polymer II-1 in Synthesis ExampleII-1 was repeated except for replacing 27 parts ofcyclohexylmethacrylate with 24 parts of dodecylmethacrylate (45% byweight) and changing 3 parts of DMAPAA into 6 parts thereof to prepare apolymer II-2.

Synthesis Examples II-3 (Polymer II-3) to II-39 (Polymer II-39) andComparative Synthesis Examples II-1 (Polymer II-40) and II-2 (PolymerII-41)

The procedure for preparation of the polymer II-1 in Synthesis ExampleII-1 was repeated except for changing the monomers having the formulae(4), (5) and (6a), and the conditions as shown in Table II-1 to preparepolymers II-3 to II-41.

Comparative Synthesis Example II-3 Preparation of Salt ofLow-Molecular-Weight Diphosphonic Acid with Alkali Metal

A low-molecular-weight 1-hydroxyethylidene-1,1-diphosphonic acid fromStrem Chemicals, Inc. was neutralized by 2 equivalents of potassiumhydroxide in methanol, and the methanol was removed. An aqueous solutionincluding 10% by weight of a salt of the1-hydroxyethylidene-1,1-diphosphonic acid had a viscosity of 2.0 mPa·sat 25° C.

TABLE II-1 (1) Monomers Monomer % by Monomer % by Monomer % by (4)weight (5) weight (6a) weight Syn. Ex. II-1 Polymer II-1 Monomer 50Cyclohexyl MA 45 DMAPAA 5 No. II-1 Syn. Ex. II-2 Polymer II-2 Monomer 50Dodecyl MA 40 DMAPAA 10 No. II-1 Syn. Ex. II-3 Polymer II-3 Monomer 50Hexadecyl MA 30 DMAPAA 20 No. II-1 Syn. Ex. II-4 Polymer II-4 Monomer 50Octadecyl MA 30 DMAPAA 20 No. II-1 Syn. Ex. II-5 Polymer II-5 Monomer 50Docosyl A 30 DMAPAA 20 No. II-1 Syn. Ex. II-6 Polymer II-6 Monomer 25Benzyl A 55 DMAPAA 20 No. II-1 Syn. Ex. II-7 Polymer II-7 Monomer 30Benzyl A 60 DMAPAA 10 No. II-1 Syn. Ex. II-8 Polymer II-8 Monomer 40Benzyl A 50 DMAPAA 10 No. II-1 Syn. Ex. II-9 Polymer II-9 Monomer 50Benzyl A 40 DMAPAA 10 No. II-1 Syn. Ex. II-10 Polymer II-10 Monomer 60Benzyl A 30 DMAPAA 10 No. II-1 Syn. Ex. II-11 Polymer II-11 Monomer 70Benzyl A 20 DMAPAA 10 No. II-1 Syn. Ex. II-12 Polymer II-12 Monomer 75Benzyl A 15 DMAPAA 10 No. II-1 Syn. Ex. II-13 Polymer II-13 Monomer 60Benzyl MA 30 DMAPAA 10 No. II-1 Syn. Ex. II-14 Polymer II-14 Monomer 50Benzyl MA 30 DMAPAA 20 No. II-1 Syn. Ex. II-15 Polymer II-15 Monomer 40Benzyl MA 50 DMAPAA 10 No. II-1 Syn. Ex. II-16 Polymer II-16 Monomer 60Dodecyl A 30 DMAPAA 10 No. II-1 Syn. Ex. II-17 Polymer II-17 Monomer 50Octadecyl A 40 DMAPAA 10 No. II-1 Syn. Ex. II-18 Polymer II-18 Monomer50 Benzyl MA 40 DMAPAA 10 No. II-1 Syn. Ex. II-19 Polymer II-19 Monomer60 Benzyl MA 30 DMAPAA 10 No. II-2 Syn. Ex. II-20 Polymer II-20 Monomer50 Benzyl MA 40 DMAPAA 10 No. II-2 Syn. Ex. II-21 Polymer II-21 Monomer50 Benzyl MA 40 DMAPAA 10 No. II-2 Syn. Ex. II-22 Polymer II-22 Monomer50 Benzyl MA 40 DMAPAA 10 No. II-3 Syn. Ex. II-23 Polymer II-23 Monomer40 Benzyl MA 40 DMAPAA 20 No. II-3 Syn. Ex. II-24 Polymer II-24 Monomer50 Benzyl MA 40 DMAPAA 10 No. II-4 Syn. Ex. II-25 Polymer II-25 Monomer60 Octadecyl MA 30 DMAPAA 10 No. II-3 Syn. Ex. II-26 Polymer II-26Monomer 50 Benzyl MA 40 DMAPAA 10 No. II-3 Syn. Ex. II-27 Polymer II-27Monomer 50 Benzyl A 47 DMAPAA 3 No. II-1 Syn. Ex. II-28 Polymer II-28Monomer 50 Benzyl A 45 DMAPAA 5 No. II-1 Syn. Ex. II-29 Polymer II-29Monomer 40 Benzyl A 30 DMAPAA 30 No. II-1 Syn. Ex. II-30 Polymer II-30Monomer 50 Benzyl A 40 DEAEAA 10 No. II-1 Syn. Ex. II-31 Polymer II-31Monomer 60 Benzyl A 30 DEAEAA 10 No. II-1 Syn. Ex. II-32 Polymer II-32Monomer 50 Benzyl MA 40 DMAPMAA 10 No. II-1 Syn. Ex. II-33 Polymer II-33Monomer 50 Benzyl A 40 DMAPMAA 10 No. II-3 Syn. Ex. II-34 Polymer II-34Monomer 40 Benzyl MA 40 DMAPMAA 20 No. II-3 Syn. Ex. II-35 Polymer II-35Monomer 50 Benzyl A 40 DMAPAA 10 No. II-1 Syn. Ex. II-36 Polymer II-36Monomer 50 Benzyl A 40 DMAPAA 10 No. II-1 Syn. Ex. II-37 Polymer II-37Monomer 50 Benzyl A 40 DMAPAA 10 No. II-1 Syn. Ex. II-38 Polymer II-38Monomer 50 Benzyl A 40 DMAPAA 10 No. II-1 Syn. Ex. II-39 Polymer II-39Monomer 50 Benzyl A 40 DMAPAA 10 No. II-5 Com. Syn. Polymer II-40Monomer 100 — 0 Ex. II-1 No. II-1 Com. Syn. Polymer II-41 Monomer 302-hydoxypropyl 70 Ex. II-2 No. II-2 acrylamide Com. Syn. Low-Neutralization of 1-hydroxyethylidene-1,1-diphosphonic Ex. II-3molecular- acid by KOH weight diphosphonic acid salt (2) Viscosity M in(mPa · s) formula (1) Syn. Ex. II-1 Polymer II-1 1.7 3Na, H Syn. Ex.II-2 Polymer II-2 1.9 3Na, H Syn. Ex. II-3 Polymer II-3 2.2 3Na, H Syn.Ex. II-4 Polymer II-4 2.1 3Na, H Syn. Ex. II-5 Polymer II-5 2.2 3Na, HSyn. Ex. II-6 Polymer II-6 1.7 3Na, H Syn. Ex. II-7 Polymer II-7 1.83Na, H Syn. Ex. II-8 Polymer II-8 1.9 3Na, H Syn. Ex. II-9 Polymer II-91.8 3Na, H Syn. Ex. II-10 Polymer II-10 2.5 3Na, H Syn. Ex. II-11Polymer II-11 2.5 3Na, H Syn. Ex. II-12 Polymer II-12 2.6 3Na, H Syn.Ex. II-13 Polymer II-13 2.5 3Na, H Syn. Ex. II-14 Polymer II-14 2.2 3Na,H Syn. Ex. II-15 Polymer II-15 2.0 3Na, H Syn. Ex. II-16 Polymer II-162.3 3Na, H Syn. Ex. II-17 Polymer II-17 2.4 3Na, H Syn. Ex. II-18Polymer II-18 1.7 2Na, 2H Syn. Ex. II-19 Polymer II-19 2.4 3K, H Syn.Ex. II-20 Polymer II-20 1.8 3K, H Syn. Ex. II-21 Polymer II-21 1.8 3K, HSyn. Ex. II-22 Polymer II-22 2.0 3Na, H Syn. Ex. II-23 Polymer II-23 2.13Na, H Syn. Ex. II-24 Polymer II-24 2.0 3TEtA, H Syn. Ex. II-25 PolymerII-25 2.5 3Na, H Syn. Ex. II-26 Polymer II-26 2.1 3Na, H Syn. Ex. II-27Polymer II-27 2.0 3Na, H Syn. Ex. II-28 Polymer II-28 2.1 3Na, H Syn.Ex. II-29 Polymer II-29 1.9 3Na, H Syn. Ex. II-30 Polymer II-30 1.9 3Na,H Syn. Ex. II-31 Polymer II-31 2.6 3Na, H Syn. Ex. II-32 Polymer II-322.0 3Na, H Syn. Ex. II-33 Polymer II-33 1.8 3Na, H Syn. Ex. II-34Polymer II-34 2.1 3Na, H Syn. Ex. II-35 Polymer II-35 1.3 3Na, H Syn.Ex. II-36 Polymer II-36 1.5 3Na, H Syn. Ex. II-37 Polymer II-37 4.0 3Na,H Syn. Ex. II-38 Polymer II-38 4.2 3Na, H Syn. Ex. II-39 Polymer II-391.7 3TetraEtA, H, H Com. Syn. Polymer II-40 3.2 2Na, 2H Ex. II-1 Com.Syn. Polymer II-41 9.5 2K, 2H Ex. II-2 Com. Syn. Low-molecular- 2.0 2K,2H Ex. II-3 weight diphosphonic acid salt

3Na. H represents M+ includes 3 Na ions and 1 proton. 2K, 2H represents2 K ions and 2 protons. TEtA represents trimethylammonium ion. MArepresents methacrylate and A represents acrylate. DEAEAA representsdiethylamino ethyl acrylamide. DMAPMAA represents dimethylaminopropylmethacrylamide. TetraEtA represents a tetraethylammonium ion andTetraBuA represents a tetrabutylammonium ion.

Synthesis Example II-42 Copolymer (Polymer II-42) Including a Salt ofPhosphonic Acid Group

In a reaction container including a gas inlet tube, a thermometer and areflux condenser, in an argon atmosphere, 193 parts ofN-dimethylformamide (DMF) were placed and heated at 75° C. In thecontainer, 223 parts of aqueous solution including 30 parts of themonomer No. II-1 as the monomer having the formula (4) and 193 parts ofwater, 212 parts of a DMF solution including 27 parts ofcyclohexylmethacrylate from Tokyo Chemical Industry Co., Ltd. as themonomer having the formula (5), 3 parts oftrimethyl-2-methacryloyloxyethyl ammonium (TMMEAC) from Tokyo ChemicalIndustry Co., Ltd. as the monomer having the formula (6b) and 182 partsof DMF, and 187.4 parts of a DMF solution including 5.4 parts of2,2′-azobisisobutylonitrile (AIBN) and 182 parts of DMF were added in 12batches every 30 min. After these were all added therein, the mixturewas further stirred for 4 hrs at 75° C., cooled and the polymerizationwas completed.

The extract was filtered, washed with hexane, and vacuum-dried at 50° C.to obtain 61 parts of a copolymer (polymer II-41).

One (1) part of the resin (copolymer) was dissolved in 100 parts ofion-exchanged water to prepare a solution, and the solution wassubjected to neutralization titration in 0.1 N of KOH methanol solutionwith thymolphthalein as an indicator to determine an acid value. Theacid value was 77 mg KOH/g. This was almost same as 77 mg KOH/gdetermined from the acid value of the monomer No. II-1 assumingcopolymerization had been made in proportion to the place-in quantity.

Based on the acid value, the copolymer was neutralized with sodiumhydroxide to prepare an aqueous solution including 10% by weight of theresin. The solution had a viscosity of 1.8 mPa·s at 25° C.

The aqueous solution including 10% by weight of the resin was used forpreparing a pigment dispersion. From the titration result of thealendronic acid (monomer material), 3 OH groups out of 4 of thephosphonic acid were proved to be neutralized by sodium ion. The resultsare shown in Table II-2.

Synthesis Example II-43 Synthesis of Polymer II-43

The procedure for preparation of the polymer II-42 in Synthesis ExampleII-42 was repeated except for replacing 27 parts ofcyclohexylmethacrylate with 24 parts of dodecylmethacrylate (45% byweight) and changing 3 parts of TMMEAC into 6 parts thereof to prepare apolymer II-43.

Synthesis Examples II-44 (Polymer II-44) to II-73 (Polymer II-75)

The procedure for preparation of the polymer II-42 in Synthesis ExampleII-42 was repeated except for changing the monomers having the formulae(4), (5) and (6b), and the conditions as shown in Table II-2 to preparepolymers II-44 to II-75.

Comparative Synthesis Example II-76 to II-78

The polymer II-40 in Comparative Synthesis Example II-1 was used as apolymer in Comparative Synthesis Example II-76, the polymer II-41 inComparative Synthesis Example II-2 was used as a polymer in ComparativeSynthesis Example II-77, and the low-molecular-weight diphosphonic acidalkali metal salt in Comparative Synthesis Example II-3 was used as adiphosphonic acid alkali metal salt in Comparative Synthesis ExampleII-78.

TABLE II-2 (1) Monomers Monomer % by Monomer % by Monomer % by (4)weight (5) weight (6b) weight Syn. Ex. II-42 Polymer II-42 Monomer 50Cyclohexyl MA 45 TMMEAC 5 No. II-1 Syn. Ex. II-43 Polymer II-43 Monomer50 Dodecyl MA 40 TMMEAC 10 No. II-1 Syn. Ex. II-44 Polymer II-44 Monomer50 Hexadecyl MA 30 TMMEAC 20 No. II-1 Syn. Ex. II-45 Polymer II-45Monomer 50 Octadecyl MA 30 TMMEAC 10 No. II-1 Syn. Ex. II-46 PolymerII-46 Monomer 50 Docosyl A 30 TMMEAC 20 No. II-1 Syn. Ex. II-47 PolymerII-47 Monomer 25 Benzyl A 55 TMMEAC 20 No. II-1 Syn. Ex. II-48 PolymerII-48 Monomer 30 Benzyl A 60 TMMEAC 10 No. II-1 Syn. Ex. II-49 PolymerII-49 Monomer 40 Benzyl A 50 TMMEAC 10 No. II-1 Syn. Ex. II-50 PolymerII-50 Monomer 50 Benzyl A 40 TMMEAC 10 No. II-1 Syn. Ex. II-51 PolymerII-51 Monomer 60 Benzyl A 30 TMMEAC 10 No. II-1 Syn. Ex. II-52 PolymerII-52 Monomer 70 Benzyl A 20 TMMEAC 10 No. II-1 Syn. Ex. II-53 PolymerII-53 Monomer 75 Benzyl A 15 TMMEAC 10 No. II-1 Syn. Ex. II-54 PolymerII-54 Monomer 60 Benzyl MA 30 TMMEAC 10 No. II-1 Syn. Ex. II-55 PolymerII-55 Monomer 50 Benzyl MA 30 TMMEAC 10 No. II-1 Syn. Ex. II-56 PolymerII-56 Monomer 40 Benzyl MA 50 TMMEAC 20 No. II-1 Syn. Ex. II-57 PolymerII-57 Monomer 60 Dodecyl A 30 TMMEAC 10 No. II-1 Syn. Ex. II-58 PolymerII-58 Monomer 50 Octadecyl A 40 TMMEAC 10 No. II-1 Syn. Ex. II-59Polymer II-59 Monomer 50 Benzyl MA 40 TMMEAC 10 No. II-1 Syn. Ex. II-60Polymer II-60 Monomer 60 Benzyl MA 30 TMMEAC 10 No. II-2 Syn. Ex. II-61Polymer II-61 Monomer 50 Benzyl MA 40 TMMEAC 10 No. II-2 Syn. Ex. II-62Polymer II-62 Monomer 50 Benzyl MA 40 TMMEAC 10 No. II-2 Syn. Ex. II-63Polymer II-63 Monomer 50 Benzyl MA 40 TMMEAC 10 No. II-3 Syn. Ex. II-64Polymer II-64 Monomer 40 Benzyl MA 40 TMMEAC 20 No. II-3 Syn. Ex. II-65Polymer II-65 Monomer 50 Benzyl MA 40 TMMEAC 10 No. II-4 Syn. Ex. II-66Polymer II-66 Monomer 60 Octadecyl MA 30 TMMEAC 10 No. II-3 Syn. Ex.II-67 Polymer II-67 Monomer 50 Benzyl MA 40 TMMEAC 10 No. II-3 Syn. Ex.II-68 Polymer II-68 Monomer 50 Benzyl A 47 TMMEAC 3 No. II-1 Syn. Ex.II-69 Polymer II-69 Monomer 50 Benzyl A 45 TMMEAC 5 No. II-1 Syn. Ex.II-70 Polymer II-70 Monomer 40 Benzyl A 30 TMMEAC 30 No. II-1 Syn. Ex.II-71 Polymer II-71 Monomer 50 Benzyl A 40 TMMEAC 10 No. II-1 Syn. Ex.II-72 Polymer II-72 Monomer 60 Benzyl A 30 TMMEAC 10 No. II-1 Syn. Ex.II-73 Polymer II-73 Monomer 50 Benzyl MA 40 TMMEAC 10 No. II-1 Syn. Ex.II-74 Polymer II-74 Monomer 50 Benzyl A 40 TMMEAC 10 No. II-3 Syn. Ex.II-75 Polymer II-75 Monomer 50 Benzyl A 40 TMMEAC 10 No. II-6 (2)Viscosity M in (mPa · s) formula (1) Syn. Ex. II-42 Polymer II-42 1.83Na, H Syn. Ex. II-43 Polymer II-43 1.8 3Na, H Syn. Ex. II-44 PolymerII-44 1.9 3Na, H Syn. Ex. II-45 Polymer II-45 2.1 3Na, H Syn. Ex. II-46Polymer II-46 2.1 3Na, H Syn. Ex. II-47 Polymer II-47 1.8 3Na, H Syn.Ex. II-48 Polymer II-48 1.8 3Na, H Syn. Ex. II-49 Polymer II-49 2.0 3Na,H Syn. Ex. II-50 Polymer II-50 2.0 3Na, H Syn. Ex. II-51 Polymer II-512.5 3Na, H Syn. Ex. II-52 Polymer II-52 2.6 3Na, H Syn. Ex. II-53Polymer II-53 2.6 3Na, H Syn. Ex. II-54 Polymer II-54 2.5 3Na, H Syn.Ex. II-55 Polymer II-55 2.3 3Na, H Syn. Ex. II-56 Polymer II-56 2.1 3Na,H Syn. Ex. II-57 Polymer II-57 2.4 3Na, H Syn. Ex. II-58 Polymer II-582.2 3Na, H Syn. Ex. II-59 Polymer II-59 1.9 2Na, 2H Syn. Ex. II-60Polymer II-60 2.2 3K, H Syn. Ex. II-61 Polymer II-61 1.9 3K, H Syn. Ex.II-62 Polymer II-62 2.1 3K, H Syn. Ex. II-63 Polymer II-63 1.9 3Na, HSyn. Ex. II-64 Polymer II-64 1.8 3Na, H Syn. Ex. II-65 Polymer II-65 2.23TEtA, H Syn. Ex. II-66 Polymer II-66 2.6 3Na, H Syn. Ex. II-67 PolymerII-67 2.2 3Na, H Syn. Ex. II-68 Polymer II-68 1.9 3Na, H Syn. Ex. II-69Polymer II-69 1.9 3Na, H Syn. Ex. II-70 Polymer II-70 2.3 3Na, H Syn.Ex. II-71 Polymer II-71 1.4 3Na, H Syn. Ex. II-72 Polymer II-72 1.5 3Na,H Syn. Ex. II-73 Polymer II-73 4.0 3Na, H Syn. Ex. II-74 Polymer II-744.4 3Na, H Syn. Ex. II-75 Polymer II-75 1.9 3TetraBuA, H

Pigment Dispersion Preparation Example Preparation of Pigment DispersionII-1

The following materials were premixed, subjected to a circulationdispersion by a disc type beads mill (KDL type from Shinmaru EnterprisesCorp., using zirconia beads having a diameter of 0.1 mm) at a peripheralspeed of 10 m/s for 10 min, and filtered with a membrane filter havingan aperture of 1.2 μm to prepare a pigment dispersion II-1.

Carbon black (NIPEX160 from Degussa AG) 20.0 Naphthalene sulfonic acidNa formalin condensate 13.0 (A-45-PN from TAKEMOTO OIL & FAT Co., Ltd.,including a solid content of 10% by weight) Pure water 67.0

Preparation of Pigment Dispersions II-2 to II-46

The procedure for preparation of the pigment dispersion II-1 wasrepeated except for changing the formulation as shown in Table II-3 toprepare pigment dispersions II-2 to I-46. The pigment dispersion II-1includes naphthalene sulfonic acid Na formalin condensate, but thepigment dispersions II-2 to I-46 do not.

TABLE II-3 (1) Solid Content Pigment Dispersion (%) II-1 II-2 II-3 II-4II-5 Naphthalene 10 13 sulfonic acid Na formalin condensate Polymer II-110 50 Polymer II-2 10 50 Polymer II-3 10 50 Polymer II-4 10 50 PolymerII-5 10 Polymer II-6 10 Polymer II-7 10 Polymer II-8 10 Polymer II-9 10Polymer II-10 10 Polymer II-11 10 Polymer II-12 10 Polymer II-13 10Polymer II-14 10 Polymer II-15 10 Polymer II-16 10 Polymer II-17 10Polymer II-18 10 Polymer II-19 10 Polymer II-20 10 Polymer II-21 10Polymer II-22 10 Polymer II-23 10 Polymer II-24 10 Polymer II-25 10Polymer II-26 10 Polymer II-27 10 Polymer II-28 10 Polymer II-29 10Polymer II-30 10 Polymer II-31 10 Polymer II-32 10 Polymer II-33 10Polymer II-34 10 Polymer II-35 10 Polymer II-36 10 Polymer II-37 10Polymer II-38 10 Polymer II-39 10 Polymer II-40 10 Polymer II-41 101-hydroxyethylidene-1,1- 10 bisphosphonic acid Carbon black (*1) — 20 2020 20 20 Pigment Blue 15:3 (*2) Pigment Red 122 (*3) — Pigment Yellow 74(*4) — Pure water — 67 30 30 30 30 Total — 100 100 100 100 100 (2) SolidContent Pigment Dispersion (%) II-6 II-7 II-8 II-9 II-10 Naphthalene 10sulfonic acid Na formalin condensate Polymer II-1 10 Polymer II-2 10Polymer II-3 10 Polymer II-4 10 Polymer II-5 10 50 Polymer II-6 10 50Polymer II-7 10 50 Polymer II-8 10 50 Polymer II-9 10 50 Polymer II-1010 Polymer II-11 10 Polymer II-12 10 Polymer II-13 10 Polymer II-14 10Polymer II-15 10 Polymer II-16 10 Polymer II-17 10 Polymer II-18 10Polymer II-19 10 Polymer II-20 10 Polymer II-21 10 Polymer II-22 10Polymer II-23 10 Polymer II-24 10 Polymer II-25 10 Polymer II-26 10Polymer II-27 10 Polymer II-28 10 Polymer II-29 10 Polymer II-30 10Polymer II-31 10 Polymer II-32 10 Polymer II-33 10 Polymer II-34 10Polymer II-35 10 Polymer II-36 10 Polymer II-37 10 Polymer II-38 10Polymer II-39 10 Polymer II-40 10 Polymer II-41 101-hydroxyethylidene-1,1- 10 bisphosphonic acid Carbon black (*1) — 20 2020 20 20 Pigment Blue 15:3 (*2) Pigment Red 122 (*3) — Pigment Yellow 74(*4) — Pure water — 67 30 30 30 30 Total — 100 100 100 100 100 (3) SolidContent Pigment Dispersion (%) II-11 II-12 II-13 II-14 II-15 Naphthalene10 sulfonic acid Na formalin condensate Polymer II-1 10 Polymer II-2 10Polymer II-3 10 Polymer II-4 10 Polymer II-5 10 Polymer II-6 10 PolymerII-7 10 Polymer II-8 10 Polymer II-9 10 50 50 50 Polymer II-10 10 50Polymer II-11 10 50 Polymer II-12 10 Polymer II-13 10 Polymer II-14 10Polymer II-15 10 Polymer II-16 10 Polymer II-17 10 Polymer II-18 10Polymer II-19 10 Polymer II-20 10 Polymer II-21 10 Polymer II-22 10Polymer II-23 10 Polymer II-24 10 Polymer II-25 10 Polymer II-26 10Polymer II-27 10 Polymer II-28 10 Polymer II-29 10 Polymer II-30 10Polymer II-31 10 Polymer II-32 10 Polymer II-33 10 Polymer II-34 10Polymer II-35 10 Polymer II-36 10 Polymer II-37 10 Polymer II-38 10Polymer II-39 10 Polymer II-40 10 Polymer II-41 101-hydroxyethylidene-1,1- 10 bisphosphonic acid Carbon black (*1) — 20 20Pigment Blue 15:3 (*2) 20 Pigment Red 122 (*3) — 20 Pigment Yellow 74(*4) — 20 Pure water — 67 30 30 30 30 Total — 100 100 100 100 100 (4)Solid Content Pigment Dispersion (%) II-16 II-17 II-18 II-19 II-20Naphthalene 10 sulfonic acid Na formalin condensate Polymer II-1 10Polymer II-2 10 Polymer II-3 10 Polymer II-4 10 Polymer II-5 10 PolymerII-6 10 Polymer II-7 10 Polymer II-8 10 Polymer II-9 10 Polymer II-10 10Polymer II-11 10 Polymer II-12 10 50 Polymer II-13 10 50 Polymer II-1410 50 Polymer II-15 10 50 Polymer II-16 10 50 Polymer II-17 10 PolymerII-18 10 Polymer II-19 10 Polymer II-20 10 Polymer II-21 10 PolymerII-22 10 Polymer II-23 10 Polymer II-24 10 Polymer II-25 10 PolymerII-26 10 Polymer II-27 10 Polymer II-28 10 Polymer II-29 10 PolymerII-30 10 Polymer II-31 10 Polymer II-32 10 Polymer II-33 10 PolymerII-34 10 Polymer II-35 10 Polymer II-36 10 Polymer II-37 10 PolymerII-38 10 Polymer II-39 10 Polymer II-40 10 Polymer II-41 101-hydroxyethylidene-1,1- 10 bisphosphonic acid Carbon black (*1) — 20 2020 20 20 Pigment Blue 15:3 (*2) Pigment Red 122 (*3) — Pigment Yellow 74(*4) — Pure water — 30 30 30 30 30 Total — 100 100 100 100 100 (5) SolidContent Pigment Dispersion (%) II-21 II-22 II-23 II-24 II-25 Naphthalene10 sulfonic acid Na formalin condensate Polymer II-1 10 Polymer II-2 10Polymer II-3 10 Polymer II-4 10 Polymer II-5 10 Polymer II-6 10 PolymerII-7 10 Polymer II-8 10 Polymer II-9 10 Polymer II-10 10 Polymer II-1110 Polymer II-12 10 Polymer II-13 10 Polymer II-14 10 Polymer II-15 10Polymer II-16 10 Polymer II-17 10 50 Polymer II-18 10 50 Polymer II-1910 50 Polymer II-20 10 50 Polymer II-21 10 50 Polymer II-22 10 PolymerII-23 10 Polymer II-24 10 Polymer II-25 10 Polymer II-26 10 PolymerII-27 10 Polymer II-28 10 Polymer II-29 10 Polymer II-30 10 PolymerII-31 10 Polymer II-32 10 Polymer II-33 10 Polymer II-34 10 PolymerII-35 10 Polymer II-36 10 Polymer II-37 10 Polymer II-38 10 PolymerII-39 10 Polymer II-40 10 Polymer II-41 10 1-hydroxyethylidene-1,1- 10bisphosphonic acid Carbon black (*1) — 20 20 20 20 20 Pigment Blue 15:3(*2) Pigment Red 122 (*3) — Pigment Yellow 74 (*4) — Pure water — 30 3030 30 30 Total — 100 100 100 100 100 (6) Solid Content PigmentDispersion (%) II-26 II-27 II-28 II-29 II-30 Naphthalene 10 sulfonicacid Na formalin condensate Polymer II-1 10 Polymer II-2 10 Polymer II-310 Polymer II-4 10 Polymer II-5 10 Polymer II-6 10 Polymer II-7 10Polymer II-8 10 Polymer II-9 10 Polymer II-10 10 Polymer II-11 10Polymer II-12 10 Polymer II-13 10 Polymer II-14 10 Polymer II-15 10Polymer II-16 10 Polymer II-17 10 Polymer II-18 10 Polymer II-19 10Polymer II-20 10 Polymer II-21 10 Polymer II-22 10 50 Polymer II-23 1050 Polymer II-24 10 50 Polymer II-25 10 50 Polymer II-26 10 50 PolymerII-27 10 Polymer II-28 10 Polymer II-29 10 Polymer II-30 10 PolymerII-31 10 Polymer II-32 10 Polymer II-33 10 Polymer II-34 10 PolymerII-35 10 Polymer II-36 10 Polymer II-37 10 Polymer II-38 10 PolymerII-39 10 Polymer II-40 10 Polymer II-41 10 1-hydroxyethylidene-1,1- 10bisphosphonic acid Carbon black (*1) — 20 20 20 20 20 Pigment Blue 15:3(*2) Pigment Red 122 (*3) — Pigment Yellow 74 (*4) — Pure water — 30 3030 30 30 Total — 100 100 100 100 100 (7) Solid Content PigmentDispersion (%) II-31 II-32 II-33 II-34 II-35 Naphthalene 10 sulfonicacid Na formalin condensate Polymer II-1 10 Polymer II-2 10 Polymer II-310 Polymer II-4 10 Polymer II-5 10 Polymer II-6 10 Polymer II-7 10Polymer II-8 10 Polymer II-9 10 Polymer II-10 10 Polymer II-11 10Polymer II-12 10 Polymer II-13 10 Polymer II-14 10 Polymer II-15 10Polymer II-16 10 Polymer II-17 10 Polymer II-18 10 Polymer II-19 10Polymer II-20 10 Polymer II-21 10 Polymer II-22 10 Polymer II-23 10Polymer II-24 10 Polymer II-25 10 Polymer II-26 10 Polymer II-27 10 50Polymer II-28 10 50 Polymer II-29 10 50 Polymer II-30 10 50 PolymerII-31 10 50 Polymer II-32 10 Polymer II-33 10 Polymer II-34 10 PolymerII-35 10 Polymer II-36 10 Polymer II-37 10 Polymer II-38 10 PolymerII-39 10 Polymer II-40 10 Polymer II-41 10 1-hydroxyethylidene-1,1- 10bisphosphonic acid Carbon black (*1) — 20 20 20 20 20 Pigment Blue 15:3(*2) Pigment Red 122 (*3) — Pigment Yellow 74 (*4) — Pure water — 30 3030 30 30 Total — 100 100 100 100 100 (8) Solid Content PigmentDispersion (%) II-36 II-37 II-38 II-39 II-40 Naphthalene 10 sulfonicacid Na formalin condensate Polymer II-1 10 Polymer II-2 10 Polymer II-310 Polymer II-4 10 Polymer II-5 10 Polymer II-6 10 Polymer II-7 10Polymer II-8 10 Polymer II-9 10 Polymer II-10 10 Polymer II-11 10Polymer II-12 10 Polymer II-13 10 Polymer II-14 10 Polymer II-15 10Polymer II-16 10 Polymer II-17 10 Polymer II-18 10 Polymer II-19 10Polymer II-20 10 Polymer II-21 10 Polymer II-22 10 Polymer II-23 10Polymer II-24 10 Polymer II-25 10 Polymer II-26 10 Polymer II-27 10Polymer II-28 10 Polymer II-29 10 Polymer II-30 10 Polymer II-31 10Polymer II-32 10 50 Polymer II-33 10 50 Polymer II-34 10 50 PolymerII-35 10 50 Polymer II-36 10 50 Polymer II-37 10 Polymer II-38 10Polymer II-39 10 Polymer II-40 10 Polymer II-41 101-hydroxyethylidene-1,1- 10 bisphosphonic acid Carbon black (*1) — 20 2020 20 20 Pigment Blue 15:3 (*2) Pigment Red 122 (*3) — Pigment Yellow 74(*4) — Pure water — 30 30 30 30 30 Total — 100 100 100 100 100 (9) SolidContent Pigment Dispersion (%) II-41 II-42 II-43 II-44 II-45 Naphthalene10 sulfonic acid Na formalin condensate Polymer II-1 10 Polymer II-2 10Polymer II-3 10 Polymer II-4 10 Polymer II-5 10 Polymer II-6 10 PolymerII-7 10 Polymer II-8 10 Polymer II-9 10 Polymer II-10 10 Polymer II-1110 Polymer II-12 10 Polymer II-13 10 Polymer II-14 10 Polymer II-15 10Polymer II-16 10 Polymer II-17 10 Polymer II-18 10 Polymer II-19 10Polymer II-20 10 Polymer II-21 10 Polymer II-22 10 Polymer II-23 10Polymer II-24 10 Polymer II-25 10 Polymer II-26 10 Polymer II-27 10Polymer II-28 10 Polymer II-29 10 Polymer II-30 10 Polymer II-31 10Polymer II-32 10 Polymer II-33 10 Polymer II-34 10 Polymer II-35 10Polymer II-36 10 Polymer II-37 10 50 Polymer II-38 10 50 Polymer II-3910 50 Polymer II-40 10 50 Polymer II-41 10 50 1-hydroxyethylidene-1,1-10 bisphosphonic acid Carbon black (*1) — 20 20 20 20 20 Pigment Blue15:3 (*2) Pigment Red 122 (*3) — Pigment Yellow 74 (*4) — Pure water —30 30 30 30 30 Total — 100 100 100 100 100 (10) Solid Content PigmentDispersion (%) II-46 Naphthalene 10 sulfonic acid Na formalin condensatePolymer II-1 10 Polymer II-2 10 Polymer II-3 10 Polymer II-4 10 PolymerII-5 10 Polymer II-6 10 Polymer II-7 10 Polymer II-8 10 Polymer II-9 10Polymer II-10 10 Polymer II-11 10 Polymer II-12 10 Polymer II-13 10Polymer II-14 10 Polymer II-15 10 Polymer II-16 10 Polymer II-17 10Polymer II-18 10 Polymer II-19 10 Polymer II-20 10 Polymer II-21 10Polymer II-22 10 Polymer II-23 10 Polymer II-24 10 Polymer II-25 10Polymer II-26 10 Polymer II-27 10 Polymer II-28 10 Polymer II-29 10Polymer II-30 10 Polymer II-31 10 Polymer II-32 10 Polymer II-33 10Polymer II-34 10 Polymer II-35 10 Polymer II-36 10 Polymer II-37 10Polymer II-38 10 Polymer II-39 10 Polymer II-40 10 Polymer II-41 101-hydroxyethylidene-1,1- 10 50 bisphosphonic acid Carbon black (*1) — 20Pigment Blue 15:3 (*2) — Pigment Red 122 (*3) — Pigment Yellow 74 (*4) —Pure water — 30 Total — 100

Preparation of Pigment Dispersion II-47

The following materials were premixed, subjected to a circulationdispersion by a disc type beads mill (KDL type from Shinmaru EnterprisesCorp., using zirconia beads having a diameter of 0.1 mm) at a peripheralspeed of 10 m/s for 10 min, and filtered with a membrane filter havingan aperture of 1.2 μm to prepare a pigment dispersion II-47.

Carbon black (NIPEX160 from Degussa AG) 20.0 Naphthalene sulfonic acidNa formalin condensate 13.0 (A-45-PN from TAKEMOTO OIL & FAT Co., Ltd.,including a solid content of 10% by weight) Pure water 67.0

Preparation of Pigment Dispersions II-48 to II-87

The procedure for preparation of the pigment dispersion II-47 wasrepeated except for changing the formulation as shown in Table II-4 toprepare pigment dispersions II-48 to II-87. The pigment dispersion II-47includes naphthalene sulfonic acid Na formalin condensate, but thepigment dispersions II-48 to I-87 do not.

TABLE II-4 Solid Content Pigment Dispersion (%) II-47 II-48 II-49 II-50II-51 Naphthalene sulfonic acid 10 13 Na formalin condensate PolymerII-42 10 50 Polymer II-43 10 50 Polymer II-44 10 50 Polymer II-45 10 50Polymer II-46 10 Polymer II-47 10 Polymer II-48 10 Polymer II-49 10Polymer II-50 10 Polymer II-51 10 Polymer II-52 10 Polymer II-53 10Polymer II-54 10 Polymer II-55 10 Polymer II-56 10 Polymer II-57 10Polymer II-58 10 Polymer II-59 10 Polymer II-60 10 Polymer II-61 10Polymer II-62 10 Polymer II-63 10 Polymer II-64 10 Polymer II-65 10Polymer II-66 10 Polymer II-67 10 Polymer II-68 10 Polymer II-69 10Polymer II-70 10 Polymer II-71 10 Polymer II-72 10 Polymer II-73 10Polymer II-74 10 Polymer II-75 10 Polymer II-76 10 Polymer II-77 101-hydroxyethylidene-1,1- 10 bisphosphonic acid Carbon black (*1) — 20 2020 20 20 Pigment Blue 15:3 (*2) Pigment Red 122 (*3) — Pigment Yellow 74(*4) — Pure water — 67 30 30 30 30 Total — 100 100 100 100 100 SolidContent Pigment Dispersion (%) II-52 II-53 II-54 II-55 II-56 Naphthalenesulfonic acid 10 Na formalin condensate Polymer II-42 10 Polymer II-4310 Polymer II-44 10 Polymer II-45 10 Polymer II-46 10 50 Polymer II-4710 50 Polymer II-48 10 50 Polymer II-49 10 50 Polymer II-50 10 50Polymer II-51 10 Polymer II-52 10 Polymer II-53 10 Polymer II-54 10Polymer II-55 10 Polymer II-56 10 Polymer II-57 10 Polymer II-58 10Polymer II-59 10 Polymer II-60 10 Polymer II-61 10 Polymer II-62 10Polymer II-63 10 Polymer II-64 10 Polymer II-65 10 Polymer II-66 10Polymer II-67 10 Polymer II-68 10 Polymer II-69 10 Polymer II-70 10Polymer II-71 10 Polymer II-72 10 Polymer II-73 10 Polymer II-74 10Polymer II-75 10 Polymer II-76 10 Polymer II-77 1-hydroxyethylidene-1,1-10 bisphosphonic acid Carbon black (*1) — 20 20 20 20 20 Pigment Blue15:3 (*2) Pigment Red 122 (*3) — Pigment Yellow 74 (*4) — Pure water —30 30 30 30 30 Total — 100 100 100 100 100 Solid Content PigmentDispersion (%) II-57 II-58 II-59 II-60 II-61 Naphthalene sulfonic acid10 Na formalin condensate Polymer II-42 10 Polymer II-43 10 PolymerII-44 10 Polymer II-45 10 Polymer II-46 10 Polymer II-47 10 PolymerII-48 10 Polymer II-49 10 Polymer II-50 10 50 50 50 Polymer II-51 10 50Polymer II-52 10 50 Polymer II-53 10 Polymer II-54 10 Polymer II-55 10Polymer II-56 10 Polymer II-57 10 Polymer II-58 10 Polymer II-59 10Polymer II-60 10 Polymer II-61 10 Polymer II-62 10 Polymer II-63 10Polymer II-64 10 Polymer II-65 10 Polymer II-66 10 Polymer II-67 10Polymer II-68 10 Polymer II-69 10 Polymer II-70 10 Polymer II-71 10Polymer II-72 10 Polymer II-73 10 Polymer II-74 10 Polymer II-75 10Polymer II-76 10 Polymer II-77 1-hydroxyethylidene-1,1- 10 bisphosphonicacid Carbon black (*1) — 20 20 20 20 20 Pigment Blue 15:3 (*2) PigmentRed 122 (*3) — Pigment Yellow 74 (*4) — Pure water — 30 30 30 30 30Total — 100 100 100 100 100 Solid Content Pigment Dispersion (%) II-62II-63 II-64 II-65 II-66 Naphthalene sulfonic acid 10 Na formalincondensate Polymer II-42 10 Polymer II-43 10 Polymer II-44 10 PolymerII-45 10 Polymer II-46 10 Polymer II-47 10 Polymer II-48 10 PolymerII-49 10 Polymer II-50 10 Polymer II-51 10 Polymer II-52 10 PolymerII-53 10 50 Polymer II-54 10 50 Polymer II-55 10 50 Polymer II-56 10 50Polymer II-57 10 50 Polymer II-58 10 Polymer II-59 10 Polymer II-60 10Polymer II-61 10 Polymer II-62 10 Polymer II-63 10 Polymer II-64 10Polymer II-65 10 Polymer II-66 10 Polymer II-67 10 Polymer II-68 10Polymer II-69 10 Polymer II-70 10 Polymer II-71 10 Polymer II-72 10Polymer II-73 10 Polymer II-74 10 Polymer II-75 10 Polymer II-76 10Polymer II-77 10 1-hydroxyethylidene-1,1- 10 bisphosphonic acid Carbonblack (*1) — 20 20 20 20 20 Pigment Blue 15:3 (*2) Pigment Red 122 (*3)— Pigment Yellow 74 (*4) — Pure water — 30 30 30 30 30 Total — 100 100100 100 100 Solid Content Pigment Dispersion (%) II-67 II-68 II-69 II-70II-71 Naphthalene sulfonic acid 10 Na formalin condensate Polymer II-4210 Polymer II-43 10 Polymer II-44 10 Polymer II-45 10 Polymer II-46 10Polymer II-47 10 Polymer II-48 10 Polymer II-49 10 Polymer II-50 10Polymer II-51 10 Polymer II-52 10 Polymer II-53 10 Polymer II-54 10Polymer II-55 10 Polymer II-56 10 Polymer II-57 10 Polymer II-58 10 50Polymer II-59 10 50 Polymer II-60 10 50 Polymer II-61 10 50 PolymerII-62 10 50 Polymer II-63 10 Polymer II-64 10 Polymer II-65 10 PolymerII-66 10 Polymer II-67 10 Polymer II-68 10 Polymer II-69 10 PolymerII-70 10 Polymer II-71 10 Polymer II-72 10 Polymer II-73 10 PolymerII-74 10 Polymer II-75 10 Polymer II-76 10 Polymer II-77 101-hydroxyethylidene-1,1- 10 bisphosphonic acid Carbon black (*1) — 20 2020 20 20 Pigment Blue 15:3 (*2) Pigment Red 122 (*3) — Pigment Yellow 74(*4) — Pure water — 30 30 30 30 30 Total — 100 100 100 100 100 SolidContent Pigment Dispersion (%) II-72 II-73 II-74 II-75 II-76 Naphthalenesulfonic acid 10 Na formalin condensate Polymer II-42 10 Polymer II-4310 Polymer II-44 10 Polymer II-45 10 Polymer II-46 10 Polymer II-47 10Polymer II-48 10 Polymer II-49 10 Polymer II-50 10 Polymer II-51 10Polymer II-52 10 Polymer II-53 10 Polymer II-54 10 Polymer II-55 10Polymer II-56 10 Polymer II-57 10 Polymer II-58 10 Polymer II-59 10Polymer II-60 10 Polymer II-61 10 Polymer II-62 10 Polymer II-63 10 50Polymer II-64 10 50 Polymer II-65 10 50 Polymer II-66 10 50 PolymerII-67 10 50 Polymer II-68 10 Polymer II-69 10 Polymer II-70 10 PolymerII-71 10 Polymer II-72 10 Polymer II-73 10 Polymer II-74 10 PolymerII-75 10 Polymer II-76 10 Polymer II-77 10 1-hydroxyethylidene-1,1- 10bisphosphonic acid Carbon black (*1) — 20 20 20 20 20 Pigment Blue 15:3(*2) Pigment Red 122 (*3) — Pigment Yellow 74 (*4) — Pure water — 30 3030 30 30 Total — 100 100 100 100 100 Solid Content Pigment Dispersion(%) II-77 II-78 II-79 II-80 II-81 Naphthalene sulfonic acid 10 Naformalin condensate Polymer II-42 10 Polymer II-43 10 Polymer II-44 10Polymer II-45 10 Polymer II-46 10 Polymer II-47 10 Polymer II-48 10Polymer II-49 10 Polymer II-50 10 Polymer II-51 10 Polymer II-52 10Polymer II-53 10 Polymer II-54 10 Polymer II-55 10 Polymer II-56 10Polymer II-57 10 Polymer II-58 10 Polymer II-59 10 Polymer II-60 10Polymer II-61 10 Polymer II-62 10 Polymer II-63 10 Polymer II-64 10Polymer II-65 10 Polymer II-66 10 Polymer II-67 10 Polymer II-68 10 50Polymer II-69 10 50 Polymer II-70 10 50 Polymer II-71 10 50 PolymerII-72 10 50 Polymer II-73 10 Polymer II-74 10 Polymer II-75 10 PolymerII-76 10 Polymer II-77 1-hydroxyethylidene-1,1- 10 bisphosphonic acidCarbon black (*1) — 20 20 20 20 20 Pigment Blue 15:3 (*2) Pigment Red122 (*3) — Pigment Yellow 74 (*4) — Pure water — 30 30 30 30 30 Total —100 100 100 100 100 Solid Content Pigment Dispersion (%) II-82 II-83II-84 II-85 II-86 Naphthalene sulfonic acid 10 Na formalin condensatePolymer II-42 10 Polymer II-43 10 Polymer II-44 10 Polymer II-45 10Polymer II-46 10 Polymer II-47 10 Polymer II-48 10 Polymer II-49 10Polymer II-50 10 Polymer II-51 10 Polymer II-52 10 Polymer II-53 10Polymer II-54 10 Polymer II-55 10 Polymer II-56 10 Polymer II-57 10Polymer II-58 10 Polymer II-59 10 Polymer II-60 10 Polymer II-61 10Polymer II-62 10 Polymer II-63 10 Polymer II-64 10 Polymer II-65 10Polymer II-66 10 Polymer II-67 10 Polymer II-68 10 Polymer II-69 10Polymer II-70 10 Polymer II-71 10 Polymer II-72 10 Polymer II-73 10 50Polymer II-74 10 50 Polymer II-75 10 50 Polymer II-76 10 50 PolymerII-77 50 1-hydroxyethylidene-1,1- 10 bisphosphonic acid Carbon black(*1) — 20 20 20 20 20 Pigment Blue 15:3 (*2) Pigment Red 122 (*3) —Pigment Yellow 74 (*4) — Pure water — 30 30 30 30 30 Total — 100 100 100100 100 Pigment Dispersion Solid Content (%) II-87 Naphthalene sulfonicacid Na 10 formalin condensate Polymer II-42 10 Polymer II-43 10 PolymerII-44 10 Polymer II-45 10 Polymer II-46 10 Polymer II-47 10 PolymerII-48 10 Polymer II-49 10 Polymer II-50 10 Polymer II-51 10 PolymerII-52 10 Polymer II-53 10 Polymer II-54 10 Polymer II-55 10 PolymerII-56 10 Polymer II-57 10 Polymer II-58 10 Polymer II-59 10 PolymerII-60 10 Polymer II-61 10 Polymer II-62 10 Polymer II-63 10 PolymerII-64 10 Polymer II-65 10 Polymer II-66 10 Polymer II-67 10 PolymerII-68 10 Polymer II-69 10 Polymer II-70 10 Polymer II-71 10 PolymerII-72 10 Polymer II-73 10 Polymer II-74 10 Polymer II-75 10 PolymerII-76 10 Polymer II-77 1-hydroxyethylidene-1,1- 10 50 bisphosphonic acidCarbon black (*1) — 20 Pigment Blue 15:3 (*2) Pigment Red 122 (*3) —Pigment Yellow 74 (*4) — Pure water — 30 Total — 100 (*1) = NIPEX 160(*2) = CHROMOFINE BLUE A-220J from Dainichiseika Color & Chemicals Mfg.Co., Ltd. (*3) = Toner Magenta E-0002 from Clariant (*4) = FAST YELLOW531 from Dainichiseika Color & Chemicals Mfg. Co., Ltd.

Preparation of Ink for Inkjet Recording Example II-1

The following materials were mixed, stirred for 1.5 hrs and filteredwith a membrane filter having an aperture of 1.2 μm to prepare an ink.

Pigment Dispersion II-1 40.0 (including a solid content of pigment in anamount of 20% by weight) 1,3-butanediol (hydrosoluble solvent) 20.0Glycerin (hydrosoluble solvent) 10.0 2-ethyl-1,3-hexanediol(hydrosoluble solvent) 1.0 2,2,4-trimethyl-1,3-pentadiol (hydrosolublesolvent) 1.0 Fluorine surfactant 2.0 (Zonyl FS-300 from DuPont includinga solid content in an amount of 40% by weight) Aqueous solution ofpolymer II-14 20.0 (including a solid content in an amount of 10% byweight) Distilled water 6.0

Example II-2

The following materials were mixed, stirred for 1.5 hrs and filteredwith a membrane filter having an aperture of 1.2 μm to prepare an ink.

Pigment Dispersion II-2 40.0 (including a solid content of pigment in anamount of 20% by weight) 1,3-butanediol (hydrosoluble solvent) 20.0Glycerin (hydrosoluble solvent) 10.0 2-ethyl-1,3-hexanediol(hydrosoluble solvent) 1.0 2,2,4-trimethyl-1,3-pentadiol (hydrosolublesolvent) 1.0 Fluorine surfactant 2.0 (Zonyl FS-300 from DuPont includinga solid content in an amount of 40% by weight) Distilled water 26.0

Examples II-3 to II-43 and Comparative Examples II-1 to II-3

The procedure for preparation of the ink in Example II-2 was repeatedexcept for changing the formulation as show in Table II-5 to prepareinks of Examples II-3 to II-43 and Comparative Examples II-1 to II-3.The ink of Example 10 is the ink of Example II-1 naphthalene sulfonicacid Na formalin condensate is excluded from and includes polymer 9 morethan Example II-1.

TABLE II-5 Example Material II-1 II-2 II-3 II-4 II-5 Pigment Naphthalene40 dispersion II-1 sulfonic acid Na Pigment Bk dispersion 40 dispersionII-2 including polymer II-1 Pigment Bk dispersion 40 dispersion II-3including polymer II-2 Pigment Bk dispersion 40 dispersion II-4including polymer II-3 Pigment Bk dispersion 40 dispersion II-5including polymer II-4 Pigment Bk dispersion dispersion II-6 includingpolymer II-5 Pigment Bk dispersion dispersion II-7 including polymerII-6 Pigment Bk dispersion dispersion II-8 including polymer II-7Pigment Bk dispersion dispersion II-9 including polymer II-8 Pigment Bkdispersion dispersion II-10 including polymer II-9 Pigment Cy dispersiondispersion II-11 including polymer II-9 Pigment Ma dispersion dispersionII-12 including polymer II-9 Pigment Ye dispersion dispersion II-13including polymer II-9 Pigment Bk dispersion dispersion II-14 includingpolymer II-10 Pigment Bk dispersion dispersion II-15 including polymerII-11 Pigment Cy dispersion dispersion II-16 including polymer II-12Pigment Ma dispersion dispersion II-17 including polymer II-13 PigmentYe dispersion dispersion II-18 including polymer II-14 Pigment Bkdispersion dispersion II-19 including polymer II-15 Pigment Bkdispersion dispersion II-20 including polymer II-16 Pigment Bkdispersion dispersion II-21 including polymer II-17 Pigment Bkdispersion dispersion II-22 including polymer II-18 Pigment Bkdispersion dispersion II-23 including polymer II-19 Pigment Bkdispersion dispersion II-24 including polymer II-20 Pigment Bkdispersion dispersion II-25 including polymer II-21 Pigment Bkdispersion dispersion II-26 including polymer I-22 Pigment Bk dispersiondispersion II-27 including polymer II-23 Pigment Bk dispersiondispersion II-28 including polymer II-24 Pigment Bk dispersiondispersion II-29 including polymer II-25 Pigment Bk dispersiondispersion II-30 including polymer II-26 Pigment Bk dispersiondispersion II-31 including polymer II-27 Pigment Bk dispersiondispersion II-32 including polymer II-28 Pigment Bk dispersiondispersion II-33 including polymer II-29 Pigment Bk dispersiondispersion II-34 including polymer II-30 Pigment Bk dispersiondispersion II-35 including polymer II-31 Pigment Bk dispersiondispersion II-36 including polymer II-32 Pigment Bk dispersiondispersion II-37 including polymer II-33 Pigment Bk dispersiondispersion II-38 including polymer II-34 Pigment Bk dispersiondispersion II-39 including polymer II-35 Pigment Bk dispersiondispersion II-40 including polymer II-36 Pigment Bk dispersiondispersion II-41 including polymer II-37 Pigment Bk dispersiondispersion II-42 including polymer II-38 Pigment Bk dispersiondispersion II-43 including polymer II-39 Pigment Bk dispersiondispersion II-44 including polymer II-40 Pigment Bk dispersiondispersion II-45 including polymer II-41 Pigment Low-molecular-dispersion II-46 weight bisphosphonic acid *1 Aqueous solution ofpolymer 20 I-14 including a solid content of 10% by weight Glycerin 1010 10 10 10 1,3-butanediol 20 20 20 20 20 2-ethyl-1,3- 1 1 1 1 1hexanediol 2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 2 2 2 22 (Zonyl FS-300) Distilled water 6 26 26 26 26 Total 100 100 100 100 100Example Material II-6 II-7 II-8 II-9 II-10 Pigment Naphthalene 40dispersion II-1 sulfonic acid Na Pigment Bk dispersion dispersion II-2including polymer II-1 Pigment Bk dispersion dispersion II-3 includingpolymer II-2 Pigment Bk dispersion dispersion II-4 including polymerII-3 Pigment Bk dispersion dispersion II-5 including polymer II-4Pigment Bk dispersion 40 dispersion II-6 including polymer II-5 PigmentBk dispersion 40 dispersion II-7 including polymer II-6 Pigment Bkdispersion 40 dispersion II-8 including polymer II-7 Pigment Bkdispersion 40 dispersion II-9 including polymer II-8 Pigment Bkdispersion 40 dispersion II-10 including polymer II-9 Pigment Cydispersion dispersion II-11 including polymer II-9 Pigment Ma dispersiondispersion II-12 including polymer II-9 Pigment Ye dispersion dispersionII-13 including polymer II-9 Pigment Bk dispersion dispersion II-14including polymer II-10 Pigment Bk dispersion dispersion II-15 includingpolymer II-11 Pigment Cy dispersion dispersion II-16 including polymerII-12 Pigment Ma dispersion dispersion II-17 including polymer II-13Pigment Ye dispersion dispersion II-18 including polymer II-14 PigmentBk dispersion dispersion II-19 including polymer II-15 Pigment Bkdispersion dispersion II-20 including polymer II-16 Pigment Bkdispersion dispersion II-21 including polymer II-17 Pigment Bkdispersion dispersion II-22 including polymer II-18 Pigment Bkdispersion dispersion II-23 including polymer II-19 Pigment Bkdispersion dispersion II-24 including polymer II-20 Pigment Bkdispersion dispersion II-25 including polymer II-21 Pigment Bkdispersion dispersion II-26 including polymer I-22 Pigment Bk dispersiondispersion II-27 including polymer II-23 Pigment Bk dispersiondispersion II-28 including polymer II-24 Pigment Bk dispersiondispersion II-29 including polymer II-25 Pigment Bk dispersiondispersion II-30 including polymer II-26 Pigment Bk dispersiondispersion II-31 including polymer II-27 Pigment Bk dispersiondispersion II-32 including polymer II-28 Pigment Bk dispersiondispersion II-33 including polymer II-29 Pigment Bk dispersiondispersion II-34 including polymer II-30 Pigment Bk dispersiondispersion II-35 including polymer II-31 Pigment Bk dispersiondispersion II-36 including polymer II-32 Pigment Bk dispersiondispersion II-37 including polymer II-33 Pigment Bk dispersiondispersion II-38 including polymer II-34 Pigment Bk dispersiondispersion II-39 including polymer II-35 Pigment Bk dispersiondispersion II-40 including polymer II-36 Pigment Bk dispersiondispersion II-41 including polymer II-37 Pigment Bk dispersiondispersion II-42 including polymer II-38 Pigment Bk dispersiondispersion II-43 including polymer II-39 Pigment Bk dispersiondispersion II-44 including polymer II-40 Pigment Bk dispersiondispersion II-45 including polymer II-41 Pigment Low-molecular-dispersion II-46 weight bisphosphonic acid *1 Aqueous solution ofpolymer I-14 including a solid content of 10% by weight Glycerin 10 1010 10 10 1,3-butanediol 20 20 20 20 20 2-ethyl-1,3- 1 1 1 1 1 hexanediol2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 2 2 2 2 2 (ZonylFS-300) Distilled water 26 26 26 26 26 Total 100 100 100 100 100 ExampleMaterial II-11 II-12 II-13 II-14 II-15 Pigment Naphthalene 40 dispersionII-1 sulfonic acid Na Pigment Bk dispersion dispersion II-2 includingpolymer II-1 Pigment Bk dispersion dispersion II-3 including polymerII-2 Pigment Bk dispersion dispersion II-4 including polymer II-3Pigment Bk dispersion dispersion II-5 including polymer II-4 Pigment Bkdispersion dispersion II-6 including polymer II-5 Pigment Bk dispersiondispersion II-7 including polymer II-6 Pigment Bk dispersion dispersionII-8 including polymer II-7 Pigment Bk dispersion dispersion II-9including polymer II-8 Pigment Bk dispersion dispersion II-10 includingpolymer II-9 Pigment Cy dispersion 40 dispersion II-11 including polymerII-9 Pigment Ma dispersion 40 dispersion II-12 including polymer II-9Pigment Ye dispersion 40 dispersion II-13 including polymer II-9 PigmentBk dispersion 40 dispersion II-14 including polymer II-10 Pigment Bkdispersion 40 dispersion II-15 including polymer II-11 Pigment Bkdispersion dispersion II-16 including polymer II-12 Pigment Bkdispersion dispersion II-17 including polymer II-13 Pigment Bkdispersion dispersion II-18 including polymer II-14 Pigment Bkdispersion dispersion II-19 including polymer II-15 Pigment Bkdispersion dispersion II-20 including polymer II-16 Pigment Bkdispersion dispersion II-21 including polymer II-17 Pigment Bkdispersion dispersion II-22 including polymer II-18 Pigment Bkdispersion dispersion II-23 including polymer II-19 Pigment Bkdispersion dispersion II-24 including polymer II-20 Pigment Bkdispersion dispersion II-25 including polymer II-21 Pigment Bkdispersion dispersion II-26 including polymer I-22 Pigment Bk dispersiondispersion II-27 including polymer II-23 Pigment Bk dispersiondispersion II-28 including polymer II-24 Pigment Bk dispersiondispersion II-29 including polymer II-25 Pigment Bk dispersiondispersion II-30 including polymer II-26 Pigment Bk dispersiondispersion II-31 including polymer II-27 Pigment Bk dispersiondispersion II-32 including polymer II-28 Pigment Bk dispersiondispersion II-33 including polymer II-29 Pigment Bk dispersiondispersion II-34 including polymer II-30 Pigment Bk dispersiondispersion II-35 including polymer II-31 Pigment Bk dispersiondispersion II-36 including polymer II-32 Pigment Bk dispersiondispersion II-37 including polymer II-33 Pigment Bk dispersiondispersion II-38 including polymer II-34 Pigment Bk dispersiondispersion II-39 including polymer II-35 Pigment Bk dispersiondispersion II-40 including polymer II-36 Pigment Bk dispersiondispersion II-41 including polymer II-37 Pigment Bk dispersiondispersion II-42 including polymer II-38 Pigment Bk dispersiondispersion II-43 including polymer II-39 Pigment Bk dispersiondispersion II-44 including polymer II-40 Pigment Bk dispersiondispersion II-45 including polymer II-41 Pigment Low-molecular-dispersion II-46 weight bisphosphonic acid *1 Aqueous solution ofpolymer I-14 including a solid content of 10% by weight Glycerin 10 1010 10 10 1,3-butanediol 20 20 20 20 20 2-ethyl-1,3- 1 1 1 1 1 hexanediol2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 2 2 2 2 2 (ZonylFS-300) Distilled water 26 26 26 26 26 Total 100 100 100 100 100 ExampleMaterial II-16 II-17 II-18 II-19 II-20 Pigment Naphthalene 40 dispersionII-1 sulfonic acid Na Pigment Bk dispersion dispersion II-2 includingpolymer II-1 Pigment Bk dispersion dispersion II-3 including polymerII-2 Pigment Bk dispersion dispersion II-4 including polymer II-3Pigment Bk dispersion dispersion II-5 including polymer II-4 Pigment Bkdispersion dispersion II-6 including polymer II-5 Pigment Bk dispersiondispersion II-7 including polymer II-6 Pigment Bk dispersion dispersionII-8 including polymer II-7 Pigment Bk dispersion dispersion II-9including polymer II-8 Pigment Bk dispersion dispersion II-10 includingpolymer II-9 Pigment Cy dispersion dispersion II-11 including polymerII-9 Pigment Ma dispersion dispersion II-12 including polymer II-9Pigment Ye dispersion dispersion II-13 including polymer II-9 Pigment Bkdispersion dispersion II-14 including polymer II-10 Pigment Bkdispersion dispersion II-15 including polymer II-11 Pigment Bkdispersion 40 dispersion II-16 including polymer II-12 Pigment Bkdispersion 40 dispersion II-17 including polymer II-13 Pigment Bkdispersion 40 dispersion II-18 including polymer II-14 Pigment Bkdispersion 40 dispersion II-19 including polymer II-15 Pigment Bkdispersion 40 dispersion II-20 including polymer II-16 Pigment Bkdispersion dispersion II-21 including polymer II-17 Pigment Bkdispersion dispersion II-22 including polymer II-18 Pigment Bkdispersion dispersion II-23 including polymer II-19 Pigment Bkdispersion dispersion II-24 including polymer II-20 Pigment Bkdispersion dispersion II-25 including polymer II-21 Pigment Bkdispersion dispersion II-26 including polymer I-22 Pigment Bk dispersiondispersion II-27 including polymer II-23 Pigment Bk dispersiondispersion II-28 including polymer II-24 Pigment Bk dispersiondispersion II-29 including polymer II-25 Pigment Bk dispersiondispersion II-30 including polymer II-26 Pigment Bk dispersiondispersion II-31 including polymer II-27 Pigment Bk dispersiondispersion II-32 including polymer II-28 Pigment Bk dispersiondispersion II-33 including polymer II-29 Pigment Bk dispersiondispersion II-34 including polymer II-30 Pigment Bk dispersiondispersion II-35 including polymer II-31 Pigment Bk dispersiondispersion II-36 including polymer II-32 Pigment Bk dispersiondispersion II-37 including polymer II-33 Pigment Bk dispersiondispersion II-38 including polymer II-34 Pigment Bk dispersiondispersion II-39 including polymer II-35 Pigment Bk dispersiondispersion II-40 including polymer II-36 Pigment Bk dispersiondispersion II-41 including polymer II-37 Pigment Bk dispersiondispersion II-42 including polymer II-38 Pigment Bk dispersiondispersion II-43 including polymer II-39 Pigment Bk dispersiondispersion II-44 including polymer II-40 Pigment Bk dispersiondispersion II-45 including polymer II-41 Pigment Low-molecular-dispersion II-46 weight bisphosphonic acid *1 Aqueous solution ofpolymer I-14 including a solid content of 10% by weight Glycerin 10 1010 10 10 1,3-butanediol 20 20 20 20 20 2-ethyl-1,3- 1 1 1 1 1 hexanediol2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 2 2 2 2 2 (ZonylFS-300) Distilled water 26 26 26 26 26 Total 100 100 100 100 100 ExampleMaterial II-21 II-22 II-23 II-24 II-25 Pigment Naphthalene 40 dispersionII-1 sulfonic acid Na Pigment Bk dispersion dispersion II-2 includingpolymer II-1 Pigment Bk dispersion dispersion II-3 including polymerII-2 Pigment Bk dispersion dispersion II-4 including polymer II-3Pigment Bk dispersion dispersion II-5 including polymer II-4 Pigment Bkdispersion dispersion II-6 including polymer II-5 Pigment Bk dispersiondispersion II-7 including polymer II-6 Pigment Bk dispersion dispersionII-8 including polymer II-7 Pigment Bk dispersion dispersion II-9including polymer II-8 Pigment Bk dispersion dispersion II-10 includingpolymer II-9 Pigment Cy dispersion dispersion II-11 including polymerII-9 Pigment Ma dispersion dispersion II-12 including polymer II-9Pigment Ye dispersion dispersion II-13 including polymer II-9 Pigment Bkdispersion dispersion II-14 including polymer II-10 Pigment Bkdispersion dispersion II-15 including polymer II-11 Pigment Bkdispersion dispersion II-16 including polymer II-12 Pigment Bkdispersion dispersion II-17 including polymer II-13 Pigment Bkdispersion dispersion II-18 including polymer II-14 Pigment Bkdispersion dispersion II-19 including polymer II-15 Pigment Bkdispersion dispersion II-20 including polymer II-16 Pigment Bkdispersion 40 dispersion II-21 including polymer II-17 Pigment Bkdispersion 40 dispersion II-22 including polymer II-18 Pigment Bkdispersion 40 dispersion II-23 including polymer II-19 Pigment Bkdispersion 40 dispersion II-24 including polymer II-20 Pigment Bkdispersion 40 dispersion II-25 including polymer II-21 Pigment Bkdispersion dispersion II-26 including polymer I-22 Pigment Bk dispersiondispersion II-27 including polymer II-23 Pigment Bk dispersiondispersion II-28 including polymer II-24 Pigment Bk dispersiondispersion II-29 including polymer II-25 Pigment Bk dispersiondispersion II-30 including polymer II-26 Pigment Bk dispersiondispersion II-31 including polymer II-27 Pigment Bk dispersiondispersion II-32 including polymer II-28 Pigment Bk dispersiondispersion II-33 including polymer II-29 Pigment Bk dispersiondispersion II-34 including polymer II-30 Pigment Bk dispersiondispersion II-35 including polymer II-31 Pigment Bk dispersiondispersion II-36 including polymer II-32 Pigment Bk dispersiondispersion II-37 including polymer II-33 Pigment Bk dispersiondispersion II-38 including polymer II-34 Pigment Bk dispersiondispersion II-39 including polymer II-35 Pigment Bk dispersiondispersion II-40 including polymer II-36 Pigment Bk dispersiondispersion II-41 including polymer II-37 Pigment Bk dispersiondispersion II-42 including polymer II-38 Pigment Bk dispersiondispersion II-43 including polymer II-39 Pigment Bk dispersiondispersion II-44 including polymer II-40 Pigment Bk dispersiondispersion II-45 including polymer II-41 Pigment Low-molecular-dispersion II-46 weight bisphosphonic acid *1 Aqueous solution ofpolymer I-14 including a solid content of 10% by weight Glycerin 10 1010 10 10 1,3-butanediol 20 20 20 20 20 2-ethyl-1,3- 1 1 1 1 1 hexanediol2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 2 2 2 2 2 (ZonylFS-300) Distilled water 26 26 26 26 26 Total 100 100 100 100 100 ExampleMaterial II-26 II-27 II-28 II-29 II-30 Pigment Naphthalene 40 dispersionII-1 sulfonic acid Na Pigment Bk dispersion dispersion II-2 includingpolymer II-1 Pigment Bk dispersion dispersion II-3 including polymerII-2 Pigment Bk dispersion dispersion II-4 including polymer II-3Pigment Bk dispersion dispersion II-5 including polymer II-4 Pigment Bkdispersion dispersion II-6 including polymer II-5 Pigment Bk dispersiondispersion II-7 including polymer II-6 Pigment Bk dispersion dispersionII-8 including polymer II-7 Pigment Bk dispersion dispersion II-9including polymer II-8 Pigment Bk dispersion dispersion II-10 includingpolymer II-9 Pigment Cy dispersion dispersion II-11 including polymerII-9 Pigment Ma dispersion dispersion II-12 including polymer II-9Pigment Ye dispersion dispersion II-13 including polymer II-9 Pigment Bkdispersion dispersion II-14 including polymer II-10 Pigment Bkdispersion dispersion II-15 including polymer II-11 Pigment Bkdispersion dispersion II-16 including polymer II-12 Pigment Bkdispersion dispersion II-17 including polymer II-13 Pigment Bkdispersion dispersion II-18 including polymer II-14 Pigment Bkdispersion dispersion II-19 including polymer II-15 Pigment Bkdispersion dispersion II-20 including polymer II-16 Pigment Bkdispersion dispersion II-21 including polymer II-17 Pigment Bkdispersion dispersion II-22 including polymer II-18 Pigment Bkdispersion dispersion II-23 including polymer II-19 Pigment Bkdispersion dispersion II-24 including polymer II-20 Pigment Bkdispersion dispersion II-25 including polymer II-21 Pigment Bkdispersion 40 dispersion II-26 including polymer I-22 Pigment Bkdispersion 40 dispersion II-27 including polymer II-23 Pigment Bkdispersion 40 dispersion II-28 including polymer II-24 Pigment Bkdispersion 40 dispersion II-29 including polymer II-25 Pigment Bkdispersion 40 dispersion II-30 including polymer II-26 Pigment Bkdispersion dispersion II-31 including polymer II-27 Pigment Bkdispersion dispersion II-32 including polymer II-28 Pigment Bkdispersion dispersion II-33 including polymer II-29 Pigment Bkdispersion dispersion II-34 including polymer II-30 Pigment Bkdispersion dispersion II-35 including polymer II-31 Pigment Bkdispersion dispersion II-36 including polymer II-32 Pigment Bkdispersion dispersion II-37 including polymer II-33 Pigment Bkdispersion dispersion II-38 including polymer II-34 Pigment Bkdispersion dispersion II-39 including polymer II-35 Pigment Bkdispersion dispersion II-40 including polymer II-36 Pigment Bkdispersion dispersion II-41 including polymer II-37 Pigment Bkdispersion dispersion II-42 including polymer II-38 Pigment Bkdispersion dispersion II-43 including polymer II-39 Pigment Bkdispersion dispersion II-44 including polymer II-40 Pigment Bkdispersion dispersion II-45 including polymer II-41 PigmentLow-molecular- dispersion II-46 weight bisphosphonic acid *1 Aqueoussolution of polymer I-14 including a solid content of 10% by weightGlycerin 10 10 10 10 10 1,3-butanediol 20 20 20 20 20 2-ethyl-1,3- 1 1 11 1 hexanediol 2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 2 22 2 2 (Zonyl FS-300) Distilled water 26 26 26 26 26 Total 100 100 100100 100 Example Material II-31 II-32 II-33 II-34 II-35 PigmentNaphthalene 40 dispersion II-1 sulfonic acid Na Pigment Bk dispersiondispersion II-2 including polymer II-1 Pigment Bk dispersion dispersionII-3 including polymer II-2 Pigment Bk dispersion dispersion II-4including polymer II-3 Pigment Bk dispersion dispersion II-5 includingpolymer II-4 Pigment Bk dispersion dispersion II-6 including polymerII-5 Pigment Bk dispersion dispersion II-7 including polymer II-6Pigment Bk dispersion dispersion II-8 including polymer II-7 Pigment Bkdispersion dispersion II-9 including polymer II-8 Pigment Bk dispersiondispersion II-10 including polymer II-9 Pigment Cy dispersion dispersionII-11 including polymer II-9 Pigment Ma dispersion dispersion II-12including polymer II-9 Pigment Ye dispersion dispersion II-13 includingpolymer II-9 Pigment Bk dispersion dispersion II-14 including polymerII-10 Pigment Bk dispersion dispersion II-15 including polymer II-11Pigment Bk dispersion dispersion II-16 including polymer II-12 PigmentBk dispersion dispersion II-17 including polymer II-13 Pigment Bkdispersion dispersion II-18 including polymer II-14 Pigment Bkdispersion dispersion II-19 including polymer II-15 Pigment Bkdispersion dispersion II-20 including polymer II-16 Pigment Bkdispersion dispersion II-21 including polymer II-17 Pigment Bkdispersion dispersion II-22 including polymer II-18 Pigment Bkdispersion dispersion II-23 including polymer II-19 Pigment Bkdispersion dispersion II-24 including polymer II-20 Pigment Bkdispersion dispersion II-25 including polymer II-21 Pigment Bkdispersion dispersion II-26 including polymer I-22 Pigment Bk dispersiondispersion II-27 including polymer II-23 Pigment Bk dispersiondispersion II-28 including polymer II-24 Pigment Bk dispersiondispersion II-29 including polymer II-25 Pigment Bk dispersiondispersion II-30 including polymer II-26 Pigment Bk dispersion 40dispersion II-31 including polymer II-27 Pigment Bk dispersion 40dispersion II-32 including polymer II-28 Pigment Bk dispersion 40dispersion II-33 including polymer II-29 Pigment Bk dispersion 40dispersion II-34 including polymer II-30 Pigment Bk dispersion 40dispersion II-35 including polymer II-31 Pigment Bk dispersiondispersion II-36 including polymer II-32 Pigment Bk dispersiondispersion II-37 including polymer II-33 Pigment Bk dispersiondispersion II-38 including polymer II-34 Pigment Bk dispersiondispersion II-39 including polymer II-35 Pigment Bk dispersiondispersion II-40 including polymer II-36 Pigment Bk dispersiondispersion II-41 including polymer II-37 Pigment Bk dispersiondispersion II-42 including polymer II-38 Pigment Bk dispersiondispersion II-43 including polymer II-39 Pigment Bk dispersiondispersion II-44 including polymer II-40 Pigment Bk dispersiondispersion II-45 including polymer II-41 Pigment Low-molecular-dispersion II-46 weight bisphosphonic acid *1 Aqueous solution ofpolymer I-14 including a solid content of 10% by weight Glycerin 10 1010 10 10 1,3-butanediol 20 20 20 20 20 2-ethyl-1,3- 1 1 1 1 1 hexanediol2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 2 2 2 2 2 (ZonylFS-300) Distilled water 26 26 26 26 26 Total 100 100 100 100 100 ExampleMaterial II-36 II-37 II-38 II-39 II-40 Pigment Naphthalene 40 dispersionII-1 sulfonic acid Na Pigment Bk dispersion dispersion II-2 includingpolymer II-1 Pigment Bk dispersion dispersion II-3 including polymerII-2 Pigment Bk dispersion dispersion II-4 including polymer II-3Pigment Bk dispersion dispersion II-5 including polymer II-4 Pigment Bkdispersion dispersion II-6 including polymer II-5 Pigment Bk dispersiondispersion II-7 including polymer II-6 Pigment Bk dispersion dispersionII-8 including polymer II-7 Pigment Bk dispersion dispersion II-9including polymer II-8 Pigment Bk dispersion dispersion II-10 includingpolymer II-9 Pigment Cy dispersion dispersion II-11 including polymerII-9 Pigment Ma dispersion dispersion II-12 including polymer II-9Pigment Ye dispersion dispersion II-13 including polymer II-9 Pigment Bkdispersion dispersion II-14 including polymer II-10 Pigment Bkdispersion dispersion II-15 including polymer II-11 Pigment Bkdispersion dispersion II-16 including polymer II-12 Pigment Bkdispersion dispersion II-17 including polymer II-13 Pigment Bkdispersion dispersion II-18 including polymer II-14 Pigment Bkdispersion dispersion II-19 including polymer II-15 Pigment Bkdispersion dispersion II-20 including polymer II-16 Pigment Bkdispersion dispersion II-21 including polymer II-17 Pigment Bkdispersion dispersion II-22 including polymer II-18 Pigment Bkdispersion dispersion II-23 including polymer II-19 Pigment Bkdispersion dispersion II-24 including polymer II-20 Pigment Bkdispersion dispersion II-25 including polymer II-21 Pigment Bkdispersion dispersion II-26 including polymer I-22 Pigment Bk dispersiondispersion II-27 including polymer II-23 Pigment Bk dispersiondispersion II-28 including polymer II-24 Pigment Bk dispersiondispersion II-29 including polymer II-25 Pigment Bk dispersiondispersion II-30 including polymer II-26 Pigment Bk dispersiondispersion II-31 including polymer II-27 Pigment Bk dispersiondispersion II-32 including polymer II-28 Pigment Bk dispersiondispersion II-33 including polymer II-29 Pigment Bk dispersiondispersion II-34 including polymer II-30 Pigment Bk dispersiondispersion II-35 including polymer II-31 Pigment Bk dispersion 40dispersion II-36 including polymer II-32 Pigment Bk dispersion 40dispersion II-37 including polymer II-33 Pigment Bk dispersion 40dispersion II-38 including polymer II-34 Pigment Bk dispersion 40dispersion II-39 including polymer II-35 Pigment Bk dispersion 40dispersion II-40 including polymer II-36 Pigment Bk dispersiondispersion II-41 including polymer II-37 Pigment Bk dispersiondispersion II-42 including polymer II-38 Pigment Bk dispersiondispersion II-43 including polymer II-39 Pigment Bk dispersiondispersion II-44 including polymer II-40 Pigment Bk dispersiondispersion II-45 including polymer II-41 Pigment Low-molecular-dispersion II-46 weight bisphosphonic acid *1 Aqueous solution ofpolymer I-14 including a solid content of 10% by weight Glycerin 10 1010 10 10 1,3-butanediol 20 20 20 20 20 2-ethyl-1,3- 1 1 1 1 1 hexanediol2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 2 2 2 2 2 (ZonylFS-300) Distilled water 26 26 26 26 26 Total 100 100 100 100 100 ExampleCom. Ex. Material II-41 II-42 II-43 II-1 II-2 Pigment Naphthalene 40dispersion II-1 sulfonic acid Na Pigment Bk dispersion dispersion II-2including polymer II-1 Pigment Bk dispersion dispersion II-3 includingpolymer II-2 Pigment Bk dispersion dispersion II-4 including polymerII-3 Pigment Bk dispersion dispersion II-5 including polymer II-4Pigment Bk dispersion dispersion II-6 including polymer II-5 Pigment Bkdispersion dispersion II-7 including polymer II-6 Pigment Bk dispersiondispersion II-8 including polymer II-7 Pigment Bk dispersion dispersionII-9 including polymer II-8 Pigment Bk dispersion dispersion II-10including polymer II-9 Pigment Cy dispersion dispersion II-11 includingpolymer II-9 Pigment Ma dispersion dispersion II-12 including polymerII-9 Pigment Ye dispersion dispersion II-13 including polymer II-9Pigment Bk dispersion dispersion II-14 including polymer II-10 PigmentBk dispersion dispersion II-15 including polymer II-11 Pigment Bkdispersion dispersion II-16 including polymer II-12 Pigment Bkdispersion dispersion II-17 including polymer II-13 Pigment Bkdispersion dispersion II-18 including polymer II-14 Pigment Bkdispersion dispersion II-19 including polymer II-15 Pigment Bkdispersion dispersion II-20 including polymer II-16 Pigment Bkdispersion dispersion II-21 including polymer II-17 Pigment Bkdispersion dispersion II-22 including polymer II-18 Pigment Bkdispersion dispersion II-23 including polymer II-19 Pigment Bkdispersion dispersion II-24 including polymer II-20 Pigment Bkdispersion dispersion II-25 including polymer II-21 Pigment Bkdispersion dispersion II-26 including polymer I-22 Pigment Bk dispersiondispersion II-27 including polymer II-23 Pigment Bk dispersiondispersion II-28 including polymer II-24 Pigment Bk dispersiondispersion II-29 including polymer II-25 Pigment Bk dispersiondispersion II-30 including polymer II-26 Pigment Bk dispersiondispersion II-31 including polymer II-27 Pigment Bk dispersiondispersion II-32 including polymer II-28 Pigment Bk dispersiondispersion II-33 including polymer II-29 Pigment Bk dispersiondispersion II-34 including polymer II-30 Pigment Bk dispersiondispersion II-35 including polymer II-31 Pigment Bk dispersiondispersion II-36 including polymer II-32 Pigment Bk dispersiondispersion II-37 including polymer II-33 Pigment Bk dispersiondispersion II-38 including polymer II-34 Pigment Bk dispersiondispersion II-39 including polymer II-35 Pigment Bk dispersiondispersion II-40 including polymer II-36 Pigment Bk dispersion 40dispersion II-41 including polymer II-37 Pigment Bk dispersion 40dispersion II-42 including polymer II-38 Pigment Bk dispersion 40dispersion II-43 including polymer II-39 Pigment Bk dispersion 40dispersion II-44 including polymer II-40 Pigment Bk dispersion 40dispersion II-45 including polymer II-41 Pigment Low-molecular-dispersion II-46 weight bisphosphonic acid *1 Aqueous solution ofpolymer I-14 including a solid content of 10% by weight Glycerin 10 1010 10 10 1,3-butanediol 20 20 20 20 20 2-ethyl-1,3- 1 1 1 1 1 hexanediol2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 2 2 2 2 2 (ZonylFS-300) Distilled water 26 26 26 26 26 Total 100 100 100 100 100 Com.Ex. Material II-3 Pigment dispersion II-1 Naphthalene sulfonic acid NaPigment dispersion II-2 Bk dispersion including polymer II-1 Pigmentdispersion II-3 Bk dispersion including polymer II-2 Pigment dispersionII-4 Bk dispersion including polymer II-3 Pigment dispersion II-5 Bkdispersion including polymer II-4 Pigment dispersion II-6 Bk dispersionincluding polymer II-5 Pigment dispersion II-7 Bk dispersion includingpolymer II-6 Pigment dispersion II-8 Bk dispersion including polymerII-7 Pigment dispersion II-9 Bk dispersion including polymer II-8Pigment dispersion II-10 Bk dispersion including polymer II-9 Pigmentdispersion II-11 Cy dispersion including polymer II-9 Pigment dispersionII-12 Ma dispersion including polymer II-9 Pigment dispersion II-13 Yedispersion including polymer II-9 Pigment dispersion II-14 Bk dispersionincluding polymer II-10 Pigment dispersion II-15 Bk dispersion includingpolymer II-11 Pigment dispersion II-16 Bk dispersion including polymerII-12 Pigment dispersion II-17 Bk dispersion including polymer II-13Pigment dispersion II-18 Bk dispersion including polymer II-14 Pigmentdispersion II-19 Bk dispersion including polymer II-15 Pigmentdispersion II-20 Bk dispersion including polymer II-16 Pigmentdispersion II-21 Bk dispersion including polymer II-17 Pigmentdispersion II-22 Bk dispersion including polymer II-18 Pigmentdispersion II-23 Bk dispersion including polymer II-19 Pigmentdispersion II-24 Bk dispersion including polymer II-20 Pigmentdispersion II-25 Bk dispersion including polymer II-21 Pigmentdispersion II-26 Bk dispersion including polymer I-22 Pigment dispersionII-27 Bk dispersion including polymer II-23 Pigment dispersion II-28 Bkdispersion including polymer II-24 Pigment dispersion II-29 Bkdispersion including polymer II-25 Pigment dispersion II-30 Bkdispersion including polymer II-26 Pigment dispersion II-31 Bkdispersion including polymer II-27 Pigment dispersion II-32 Bkdispersion including polymer II-28 Pigment dispersion II-33 Bkdispersion including polymer II-29 Pigment dispersion II-34 Bkdispersion including polymer II-30 Pigment dispersion II-35 Bkdispersion including polymer II-31 Pigment dispersion II-36 Bkdispersion including polymer II-32 Pigment dispersion II-37 Bkdispersion including polymer II-33 Pigment dispersion II-38 Bkdispersion including polymer II-34 Pigment dispersion II-39 Bkdispersion including polymer II-35 Pigment dispersion II-40 Bkdispersion including polymer II-36 Pigment dispersion II-41 Bkdispersion including polymer II-37 Pigment dispersion II-42 Bkdispersion including polymer II-38 Pigment dispersion II-43 Bkdispersion including polymer II-39 Pigment dispersion II-44 Bkdispersion including polymer II-40 Pigment dispersion II-45 Bkdispersion including polymer II-41 Pigment dispersion II-46Low-molecular-weight bisphosphonic 40 acid *1 Aqueous solution ofpolymer I-14 including a solid content of 10% by weight Glycerin 101,3-butanediol 20 2-ethyl-1,3-hexanediol 1 2,2,4-trimethyl-1,3-pentadiol1 Surfactant (Zonyl FS-300) 2 Distilled water 26 Total 100 *1:Low-molecular-weight bisphosphonic acid =1-hydroxyethylidene-1,1-bisphosphonic acid

Example II-44

The following materials were mixed, stirred for 1.5 hrs and filteredwith a membrane filter having an aperture of 1.2 μm to prepare an ink.

Pigment Dispersion II-47 40.0 (including a solid content of pigment inan amount of 20% by weight) 1,3-butanediol (hydrosoluble solvent) 20.0Glycerin (hydrosoluble solvent) 10.0 2-ethyl-1,3-hexanediol(hydrosoluble solvent) 1.0 2,2,4-trimethyl-1,3-pentadiol (hydrosolublesolvent) 1.0 Fluorine surfactant 2.0 (Zonyl FS-300 from DuPont includinga solid content in an amount of 40% by weight) Aqueous solution ofpolymer II-14 20.0 (including a solid content in an amount of 10% byweight) Distilled water 6.0

Example II-45

The following materials were mixed, stirred for 1.5 hrs and filteredwith a membrane filter having an aperture of 1.2 μm to prepare an ink.

Pigment Dispersion II-48 40.0 (including a solid content of pigment inan amount of 20% by weight) 1,3-butanediol (hydrosoluble solvent) 20.0Glycerin (hydrosoluble solvent) 10.0 2-ethyl-1,3-hexanediol(hydrosoluble solvent) 1.0 2,2,4-trimethyl-1,3-pentadiol (hydrosolublesolvent) 1.0 Fluorine surfactant 2.0 (Zonyl FS-300 from DuPont includinga solid content in an amount of 40% by weight) Distilled water 26.0

Examples II-46 to II-81 and Comparative Examples II-4 to II-6

The procedure for preparation of the ink in Example II-45 was repeatedexcept for changing the formulation as show in Table II-6 to prepareinks of Examples II-46 to II-81 and Comparative Examples II-4 to II-6.The ink of Example 53 is the ink of Example II-44 naphthalene sulfonicacid Na formalin condensate is excluded from.

TABLE II-6 (1) Example Material II-44 II-45 II-46 II-47 II-48 PigmentNaphthalene 40 dispersion II-47 sulfonic acid Na Pigment Bk dispersion40 dispersion II-48 including polymer II-42 Pigment Bk dispersion 40dispersion II-49 including polymer II-43 Pigment Bk dispersion 40dispersion II-50 including polymer II-44 Pigment Bk dispersion 40dispersion II-51 including polymer II-45 Pigment Bk dispersiondispersion II-52 including polymer II-46 Pigment Bk dispersiondispersion II-53 including polymer II-47 Pigment Bk dispersiondispersion II-54 including polymer II-48 Pigment Bk dispersiondispersion II-55 including polymer II-49 Pigment Cy dispersiondispersion II-56 including polymer II-49 Pigment Ma dispersiondispersion II-57 including polymer II-49 Pigment Ye dispersiondispersion II-58 including polymer II-49 Pigment Bk dispersiondispersion II-59 including polymer II-50 Pigment Bk dispersiondispersion II-60 including polymer II-51 Pigment Bk dispersiondispersion II-61 including polymer II-52 Pigment Bk dispersiondispersion II-62 including polymer II-53 Pigment Bk dispersiondispersion II-63 including polymer II-54 Pigment Bk dispersiondispersion II-64 including polymer II-55 Pigment Bk dispersiondispersion II-65 including polymer II-56 Pigment Bk dispersiondispersion II-66 including polymer II-57 Pigment Bk dispersiondispersion II-67 including polymer II-58 Pigment Bk dispersiondispersion II-68 including polymer II-59 Pigment Bk dispersiondispersion II-69 including polymer II-60 Pigment Bk dispersiondispersion II-70 including polymer II-61 Pigment Bk dispersiondispersion II-71 including polymer II-62 Pigment Bk dispersiondispersion II-72 including polymer II-63 Pigment Bk dispersiondispersion II-73 including polymer II-64 Pigment Bk dispersiondispersion II-74 including polymer II-65 Pigment Bk dispersiondispersion II-75 including polymer II-66 Pigment Bk dispersiondispersion II-76 including polymer II-67 Pigment Bk dispersiondispersion II-77 including polymer II-68 Pigment Bk dispersiondispersion II-78 including polymer II-69 Pigment Bk dispersiondispersion II-79 including polymer II-70 Pigment Bk dispersiondispersion II-80 including polymer II-71 Pigment Bk dispersiondispersion II-81 including polymer II-72 Pigment Bk dispersiondispersion II-82 including polymer II-73 Pigment Bk dispersiondispersion II-83 including polymer II-74 Pigment Bk dispersiondispersion II-84 including polymer II-75 Pigment Bk dispersiondispersion II-85 including polymer II-76 Pigment Bk dispersiondispersion II-86 including polymer II-77 Pigment Low-molecular-dispersion II-87 weight bisphosphonic acid *1 Aqueous solution ofpolymer 20 I-14 including a solid content of 10% by weight Glycerin 1010 10 10 10 1,3-butanediol 20 20 20 20 20 2-ethyl-1,3- 1 1 1 1 1hexanediol 2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 2 2 2 22 (Zonyl FS-300) Distilled water 6 26 26 26 26 Total 100 100 100 100 100(2) Example Material II-49 II-50 II-51 II-52 II-53 Pigment Naphthalenedispersion II-47 sulfonic acid Na Pigment Bk dispersion dispersion II-48including polymer II-42 Pigment Bk dispersion dispersion II-49 includingpolymer II-43 Pigment Bk dispersion dispersion II-50 including polymerII-44 Pigment Bk dispersion dispersion II-51 including polymer II-45Pigment Bk dispersion 40 dispersion II-52 including polymer II-46Pigment Bk dispersion 40 dispersion II-53 including polymer II-47Pigment Bk dispersion 40 dispersion II-54 including polymer II-48Pigment Bk dispersion 40 dispersion II-55 including polymer II-49Pigment Cy dispersion 40 dispersion II-56 including polymer II-49Pigment Ma dispersion dispersion II-57 including polymer II-49 PigmentYe dispersion dispersion II-58 including polymer II-49 Pigment Bkdispersion dispersion II-59 including polymer II-50 Pigment Bkdispersion dispersion II-60 including polymer II-51 Pigment Bkdispersion dispersion II-61 including polymer II-52 Pigment Bkdispersion dispersion II-62 including polymer II-53 Pigment Bkdispersion dispersion II-63 including polymer II-54 Pigment Bkdispersion dispersion II-64 including polymer II-55 Pigment Bkdispersion dispersion II-65 including polymer II-56 Pigment Bkdispersion dispersion II-66 including polymer II-57 Pigment Bkdispersion dispersion II-67 including polymer II-58 Pigment Bkdispersion dispersion II-68 including polymer II-59 Pigment Bkdispersion dispersion II-69 including polymer II-60 Pigment Bkdispersion dispersion II-70 including polymer II-61 Pigment Bkdispersion dispersion II-71 including polymer II-62 Pigment Bkdispersion dispersion II-72 including polymer II-63 Pigment Bkdispersion dispersion II-73 including polymer II-64 Pigment Bkdispersion dispersion II-74 including polymer II-65 Pigment Bkdispersion dispersion II-75 including polymer II-66 Pigment Bkdispersion dispersion II-76 including polymer II-67 Pigment Bkdispersion dispersion II-77 including polymer II-68 Pigment Bkdispersion dispersion II-78 including polymer II-69 Pigment Bkdispersion dispersion II-79 including polymer II-70 Pigment Bkdispersion dispersion II-80 including polymer II-71 Pigment Bkdispersion dispersion II-81 including polymer II-72 Pigment Bkdispersion dispersion II-82 including polymer II-73 Pigment Bkdispersion dispersion II-83 including polymer II-74 Pigment Bkdispersion dispersion II-84 including polymer II-75 Pigment Bkdispersion dispersion II-85 including polymer II-76 Pigment Bkdispersion dispersion II-86 including polymer II-77 PigmentLow-molecular- dispersion II-87 weight bisphosphonic acid *1 Aqueoussolution of polymer I-14 including a solid content of 10% by weightGlycerin 10 10 10 10 10 1,3-butanediol 20 20 20 20 20 2-ethyl-1,3- 1 1 11 1 hexanediol 2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 2 22 2 2 (Zonyl FS-300) Distilled water 26 26 26 26 26 Total 100 100 100100 100 (3) Example Material II-54 II-55 II-56 II-57 II-58 PigmentNaphthalene dispersion II-47 sulfonic acid Na Pigment Bk dispersiondispersion II-48 including polymer II-42 Pigment Bk dispersiondispersion II-49 including polymer II-43 Pigment Bk dispersiondispersion II-50 including polymer II-44 Pigment Bk dispersiondispersion II-51 including polymer II-45 Pigment Bk dispersiondispersion II-52 including polymer II-46 Pigment Bk dispersiondispersion II-53 including polymer II-47 Pigment Bk dispersiondispersion II-54 including polymer II-48 Pigment Bk dispersiondispersion II-55 including polymer II-49 Pigment Cy dispersiondispersion II-56 including polymer II-49 Pigment Ma dispersion 40dispersion II-57 including polymer II-49 Pigment Ye dispersion 40dispersion II-58 including polymer II-49 Pigment Bk dispersion 40dispersion II-59 including polymer II-50 Pigment Bk dispersion 40dispersion II-60 including polymer II-51 Pigment Bk dispersion 40dispersion II-61 including polymer II-52 Pigment Bk dispersiondispersion II-62 including polymer II-53 Pigment Bk dispersiondispersion II-63 including polymer II-54 Pigment Bk dispersiondispersion II-64 including polymer II-55 Pigment Bk dispersiondispersion II-65 including polymer II-56 Pigment Bk dispersiondispersion II-66 including polymer II-57 Pigment Bk dispersiondispersion II-67 including polymer II-58 Pigment Bk dispersiondispersion II-68 including polymer II-59 Pigment Bk dispersiondispersion II-69 including polymer II-60 Pigment Bk dispersiondispersion II-70 including polymer II-61 Pigment Bk dispersiondispersion II-71 including polymer II-62 Pigment Bk dispersiondispersion II-72 including polymer II-63 Pigment Bk dispersiondispersion II-73 including polymer II-64 Pigment Bk dispersiondispersion II-74 including polymer II-65 Pigment Bk dispersiondispersion II-75 including polymer II-66 Pigment Bk dispersiondispersion II-76 including polymer II-67 Pigment Bk dispersiondispersion II-77 including polymer II-68 Pigment Bk dispersiondispersion II-78 including polymer II-69 Pigment Bk dispersiondispersion II-79 including polymer II-70 Pigment Bk dispersiondispersion II-80 including polymer II-71 Pigment Bk dispersiondispersion II-81 including polymer II-72 Pigment Bk dispersiondispersion II-82 including polymer II-73 Pigment Bk dispersiondispersion II-83 including polymer II-74 Pigment Bk dispersiondispersion II-84 including polymer II-75 Pigment Bk dispersiondispersion II-85 including polymer II-76 Pigment Bk dispersiondispersion II-86 including polymer II-77 Pigment Low-molecular-dispersion II-87 weight bisphosphonic acid *1 Aqueous solution ofpolymer I-14 including a solid content of 10% by weight Glycerin 10 1010 10 10 1,3-butanediol 20 20 20 20 20 2-ethyl-1,3- 1 1 1 1 1 hexanediol2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 2 2 2 2 2 (ZonylFS-300) Distilled water 26 26 26 26 26 Total 100 100 100 100 100 (4)Example Material II-59 II-60 II-61 II-62 II-63 Pigment Naphthalenedispersion II-47 sulfonic acid Na Pigment Bk dispersion dispersion II-48including polymer II-42 Pigment Bk dispersion dispersion II-49 includingpolymer II-43 Pigment Bk dispersion dispersion II-50 including polymerII-44 Pigment Bk dispersion dispersion II-51 including polymer II-45Pigment Bk dispersion dispersion II-52 including polymer II-46 PigmentBk dispersion dispersion II-53 including polymer II-47 Pigment Bkdispersion dispersion II-54 including polymer II-48 Pigment Bkdispersion dispersion II-55 including polymer II-49 Pigment Cydispersion dispersion II-56 including polymer II-49 Pigment Madispersion dispersion II-57 including polymer II-49 Pigment Yedispersion dispersion II-58 including polymer II-49 Pigment Bkdispersion dispersion II-59 including polymer II-50 Pigment Bkdispersion dispersion II-60 including polymer II-51 Pigment Bkdispersion dispersion II-61 including polymer II-52 Pigment Bkdispersion 40 dispersion II-62 including polymer II-53 Pigment Bkdispersion 40 dispersion II-63 including polymer II-54 Pigment Bkdispersion 40 dispersion II-64 including polymer II-55 Pigment Bkdispersion 40 dispersion II-65 including polymer II-56 Pigment Bkdispersion 40 dispersion II-66 including polymer II-57 Pigment Bkdispersion dispersion II-67 including polymer II-58 Pigment Bkdispersion dispersion II-68 including polymer II-59 Pigment Bkdispersion dispersion II-69 including polymer II-60 Pigment Bkdispersion dispersion II-70 including polymer II-61 Pigment Bkdispersion dispersion II-71 including polymer II-62 Pigment Bkdispersion dispersion II-72 including polymer II-63 Pigment Bkdispersion dispersion II-73 including polymer II-64 Pigment Bkdispersion dispersion II-74 including polymer II-65 Pigment Bkdispersion dispersion II-75 including polymer II-66 Pigment Bkdispersion dispersion II-76 including polymer II-67 Pigment Bkdispersion dispersion II-77 including polymer II-68 Pigment Bkdispersion dispersion II-78 including polymer II-69 Pigment Bkdispersion dispersion II-79 including polymer II-70 Pigment Bkdispersion dispersion II-80 including polymer II-71 Pigment Bkdispersion dispersion II-81 including polymer II-72 Pigment Bkdispersion dispersion II-82 including polymer II-73 Pigment Bkdispersion dispersion II-83 including polymer II-74 Pigment Bkdispersion dispersion II-84 including polymer II-75 Pigment Bkdispersion dispersion II-85 including polymer II-76 Pigment Bkdispersion dispersion II-86 including polymer II-77 PigmentLow-molecular- dispersion II-87 weight bisphosphonic acid *1 Aqueoussolution of polymer I-14 including a solid content of 10% by weightGlycerin 10 10 10 10 10 1,3-butanediol 20 20 20 20 20 2-ethyl-1,3- 1 1 11 1 hexanediol 2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 2 22 2 2 (Zonyl FS-300) Distilled water 26 26 26 26 26 Total 100 100 100100 100 (5) Example Material II-64 II-65 II-66 II-67 II-68 PigmentNaphthalene dispersion II-47 sulfonic acid Na Pigment Bk dispersiondispersion II-48 including polymer II-42 Pigment Bk dispersiondispersion II-49 including polymer II-43 Pigment Bk dispersiondispersion II-50 including polymer II-44 Pigment Bk dispersiondispersion II-51 including polymer II-45 Pigment Bk dispersiondispersion II-52 including polymer II-46 Pigment Bk dispersiondispersion II-53 including polymer II-47 Pigment Bk dispersiondispersion II-54 including polymer II-48 Pigment Bk dispersiondispersion II-55 including polymer II-49 Pigment Cy dispersiondispersion II-56 including polymer II-49 Pigment Ma dispersiondispersion II-57 including polymer II-49 Pigment Ye dispersiondispersion II-58 including polymer II-49 Pigment Bk dispersiondispersion II-59 including polymer II-50 Pigment Bk dispersiondispersion II-60 including polymer II-51 Pigment Bk dispersiondispersion II-61 including polymer II-52 Pigment Bk dispersiondispersion II-62 including polymer II-53 Pigment Bk dispersiondispersion II-63 including polymer II-54 Pigment Bk dispersiondispersion II-64 including polymer II-55 Pigment Bk dispersiondispersion II-65 including polymer II-56 Pigment Bk dispersiondispersion II-66 including polymer II-57 Pigment Bk dispersion 40dispersion II-67 including polymer II-58 Pigment Bk dispersion 40dispersion II-68 including polymer II-59 Pigment Bk dispersion 40dispersion II-69 including polymer II-60 Pigment Bk dispersion 40dispersion II-70 including polymer II-61 Pigment Bk dispersion 40dispersion II-71 including polymer II-62 Pigment Bk dispersiondispersion II-72 including polymer II-63 Pigment Bk dispersiondispersion II-73 including polymer II-64 Pigment Bk dispersiondispersion II-74 including polymer II-65 Pigment Bk dispersiondispersion II-75 including polymer II-66 Pigment Bk dispersiondispersion II-76 including polymer II-67 Pigment Bk dispersiondispersion II-77 including polymer II-68 Pigment Bk dispersiondispersion II-78 including polymer II-69 Pigment Bk dispersiondispersion II-79 including polymer II-70 Pigment Bk dispersiondispersion II-80 including polymer II-71 Pigment Bk dispersiondispersion II-81 including polymer II-72 Pigment Bk dispersiondispersion II-82 including polymer II-73 Pigment Bk dispersiondispersion II-83 including polymer II-74 Pigment Bk dispersiondispersion II-84 including polymer II-75 Pigment Bk dispersiondispersion II-85 including polymer II-76 Pigment Bk dispersiondispersion II-86 including polymer II-77 Pigment Low-molecular-dispersion II-87 weight bisphosphonic acid *1 Aqueous solution ofpolymer I-14 including a solid content of 10% by weight Glycerin 10 1010 10 10 1,3-butanediol 20 20 20 20 20 2-ethyl-1,3- 1 1 1 1 1 hexanediol2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 2 2 2 2 2 (ZonylFS-300) Distilled water 26 26 26 26 26 Total 100 100 100 100 100 (6)Example Material II-69 II-70 II-71 II-72 II-73 Pigment Naphthalenedispersion II-47 sulfonic acid Na Pigment Bk dispersion dispersion II-48including polymer II-42 Pigment Bk dispersion dispersion II-49 includingpolymer II-43 Pigment Bk dispersion dispersion II-50 including polymerII-44 Pigment Bk dispersion dispersion II-51 including polymer II-45Pigment Bk dispersion dispersion II-52 including polymer II-46 PigmentBk dispersion dispersion II-53 including polymer II-47 Pigment Bkdispersion dispersion II-54 including polymer II-48 Pigment Bkdispersion dispersion II-55 including polymer II-49 Pigment Cydispersion dispersion II-56 including polymer II-49 Pigment Madispersion dispersion II-57 including polymer II-49 Pigment Yedispersion dispersion II-58 including polymer II-49 Pigment Bkdispersion dispersion II-59 including polymer II-50 Pigment Bkdispersion dispersion II-60 including polymer II-51 Pigment Bkdispersion dispersion II-61 including polymer II-52 Pigment Bkdispersion dispersion II-62 including polymer II-53 Pigment Bkdispersion dispersion II-63 including polymer II-54 Pigment Bkdispersion dispersion II-64 including polymer II-55 Pigment Bkdispersion dispersion II-65 including polymer II-56 Pigment Bkdispersion dispersion II-66 including polymer II-57 Pigment Bkdispersion dispersion II-67 including polymer II-58 Pigment Bkdispersion dispersion II-68 including polymer II-59 Pigment Bkdispersion dispersion II-69 including polymer II-60 Pigment Bkdispersion dispersion II-70 including polymer II-61 Pigment Bkdispersion dispersion II-71 including polymer II-62 Pigment Bkdispersion 40 dispersion II-72 including polymer II-63 Pigment Bkdispersion 40 dispersion II-73 including polymer II-64 Pigment Bkdispersion 40 dispersion II-74 including polymer II-65 Pigment Bkdispersion 40 dispersion II-75 including polymer II-66 Pigment Bkdispersion 40 dispersion II-76 including polymer II-67 Pigment Bkdispersion dispersion II-77 including polymer II-68 Pigment Bkdispersion dispersion II-78 including polymer II-69 Pigment Bkdispersion dispersion II-79 including polymer II-70 Pigment Bkdispersion dispersion II-80 including polymer II-71 Pigment Bkdispersion dispersion II-81 including polymer II-72 Pigment Bkdispersion dispersion II-82 including polymer II-73 Pigment Bkdispersion dispersion II-83 including polymer II-74 Pigment Bkdispersion dispersion II-84 including polymer II-75 Pigment Bkdispersion dispersion II-85 including polymer II-76 Pigment Bkdispersion dispersion II-86 including polymer II-77 PigmentLow-molecular- dispersion II-87 weight bisphosphonic acid *1 Aqueoussolution of polymer I-14 including a solid content of 10% by weightGlycerin 10 10 10 10 10 1,3-butanediol 20 20 20 20 20 2-ethyl-1,3- 1 1 11 1 hexanediol 2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 2 22 2 2 (Zonyl FS-300) Distilled water 26 26 26 26 26 Total 100 100 100100 100 (7) Example Material II-74 II-75 II-76 II-77 II-78 PigmentNaphthalene dispersion II-47 sulfonic acid Na Pigment Bk dispersiondispersion II-48 including polymer II-42 Pigment Bk dispersiondispersion II-49 including polymer II-43 Pigment Bk dispersiondispersion II-50 including polymer II-44 Pigment Bk dispersiondispersion II-51 including polymer II-45 Pigment Bk dispersiondispersion II-52 including polymer II-46 Pigment Bk dispersiondispersion II-53 including polymer II-47 Pigment Bk dispersiondispersion II-54 including polymer II-48 Pigment Bk dispersiondispersion II-55 including polymer II-49 Pigment Cy dispersiondispersion II-56 including polymer II-49 Pigment Ma dispersiondispersion II-57 including polymer II-49 Pigment Ye dispersiondispersion II-58 including polymer II-49 Pigment Bk dispersiondispersion II-59 including polymer II-50 Pigment Bk dispersiondispersion II-60 including polymer II-51 Pigment Bk dispersiondispersion II-61 including polymer II-52 Pigment Bk dispersiondispersion II-62 including polymer II-53 Pigment Bk dispersiondispersion II-63 including polymer II-54 Pigment Bk dispersiondispersion II-64 including polymer II-55 Pigment Bk dispersiondispersion II-65 including polymer II-56 Pigment Bk dispersiondispersion II-66 including polymer II-57 Pigment Bk dispersiondispersion II-67 including polymer II-58 Pigment Bk dispersiondispersion II-68 including polymer II-59 Pigment Bk dispersiondispersion II-69 including polymer II-60 Pigment Bk dispersiondispersion II-70 including polymer II-61 Pigment Bk dispersiondispersion II-71 including polymer II-62 Pigment Bk dispersiondispersion II-72 including polymer II-63 Pigment Bk dispersiondispersion II-73 including polymer II-64 Pigment Bk dispersiondispersion II-74 including polymer II-65 Pigment Bk dispersiondispersion II-75 including polymer II-66 Pigment Bk dispersiondispersion II-76 including polymer II-67 Pigment Bk dispersion 40dispersion II-77 including polymer II-68 Pigment Bk dispersion 40dispersion II-78 including polymer II-69 Pigment Bk dispersion 40dispersion II-79 including polymer II-70 Pigment Bk dispersion 40dispersion II-80 including polymer II-71 Pigment Bk dispersion 40dispersion II-81 including polymer II-72 Pigment Bk dispersiondispersion II-82 including polymer II-73 Pigment Bk dispersiondispersion II-83 including polymer II-74 Pigment Bk dispersiondispersion II-84 including polymer II-75 Pigment Bk dispersiondispersion II-85 including polymer II-76 Pigment Bk dispersiondispersion II-86 including polymer II-77 Pigment Low-molecular-dispersion II-87 weight bisphosphonic acid *1 Aqueous solution ofpolymer I-14 including a solid content of 10% by weight Glycerin 10 1010 10 10 1,3-butanediol 20 20 20 20 20 2-ethyl-1,3- 1 1 1 1 1 hexanediol2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 2 2 2 2 2 (ZonylFS-300) Distilled water 26 26 26 26 26 Total 100 100 100 100 100 (8)Example Com. Ex. Material II-79 II-80 II-81 II-4 II-5 PigmentNaphthalene dispersion II-47 sulfonic acid Na Pigment Bk dispersiondispersion II-48 including polymer II-42 Pigment Bk dispersiondispersion II-49 including polymer II-43 Pigment Bk dispersiondispersion II-50 including polymer II-44 Pigment Bk dispersiondispersion II-51 including polymer II-45 Pigment Bk dispersiondispersion II-52 including polymer II-46 Pigment Bk dispersiondispersion II-53 including polymer II-47 Pigment Bk dispersiondispersion II-54 including polymer II-48 Pigment Bk dispersiondispersion II-55 including polymer II-49 Pigment Cy dispersiondispersion II-56 including polymer II-49 Pigment Ma dispersiondispersion II-57 including polymer II-49 Pigment Ye dispersiondispersion II-58 including polymer II-49 Pigment Bk dispersiondispersion II-59 including polymer II-50 Pigment Bk dispersiondispersion II-60 including polymer II-51 Pigment Bk dispersiondispersion II-61 including polymer II-52 Pigment Bk dispersiondispersion II-62 including polymer II-53 Pigment Bk dispersiondispersion II-63 including polymer II-54 Pigment Bk dispersiondispersion II-64 including polymer II-55 Pigment Bk dispersiondispersion II-65 including polymer II-56 Pigment Bk dispersiondispersion II-66 including polymer II-57 Pigment Bk dispersiondispersion II-67 including polymer II-58 Pigment Bk dispersiondispersion II-68 including polymer II-59 Pigment Bk dispersiondispersion II-69 including polymer II-60 Pigment Bk dispersiondispersion II-70 including polymer II-61 Pigment Bk dispersiondispersion II-71 including polymer II-62 Pigment Bk dispersiondispersion II-72 including polymer II-63 Pigment Bk dispersiondispersion II-73 including polymer II-64 Pigment Bk dispersiondispersion II-74 including polymer II-65 Pigment Bk dispersiondispersion II-75 including polymer II-66 Pigment Bk dispersiondispersion II-76 including polymer II-67 Pigment Bk dispersiondispersion II-77 including polymer II-68 Pigment Bk dispersiondispersion II-78 including polymer II-69 Pigment Bk dispersiondispersion II-79 including polymer II-70 Pigment Bk dispersiondispersion II-80 including polymer II-71 Pigment Bk dispersiondispersion II-81 including polymer II-72 Pigment Bk dispersion 40dispersion II-82 including polymer II-73 Pigment Bk dispersion 40dispersion II-83 including polymer II-74 Pigment Bk dispersion 40dispersion II-84 including polymer II-75 Pigment Bk dispersion 40dispersion II-85 including polymer II-76 Pigment Bk dispersion 40dispersion II-86 including polymer II-77 Pigment Low-molecular-dispersion II-87 weight bisphosphonic acid *1 Aqueous solution ofpolymer I-14 including a solid content of 10% by weight Glycerin 10 1010 10 10 1,3-butanediol 20 20 20 20 20 2-ethyl-1,3- 1 1 1 1 1 hexanediol2,2,4- 1 1 1 1 1 trimethyl-1,3- pentadiol Surfactant 2 2 2 2 2 (ZonylFS-300) Distilled water 26 26 26 26 26 Total 100 100 100 100 100 (9)Com. Ex. Material II-79 Pigment dispersion II-47 Naphthalene sulfonicacid Na Pigment dispersion II-48 Bk dispersion including polymer II-42Pigment dispersion II-49 Bk dispersion including polymer II-43 Pigmentdispersion II-50 Bk dispersion including polymer II-44 Pigmentdispersion II-51 Bk dispersion including polymer II-45 Pigmentdispersion II-52 Bk dispersion including polymer II-46 Pigmentdispersion II-53 Bk dispersion including polymer II-47 Pigmentdispersion II-54 Bk dispersion including polymer II-48 Pigmentdispersion II-55 Bk dispersion including polymer II-49 Pigmentdispersion II-56 Cy dispersion including polymer II-49 Pigmentdispersion II-57 Ma dispersion including polymer II-49 Pigmentdispersion II-58 Ye dispersion including polymer II-49 Pigmentdispersion II-59 Bk dispersion including polymer II-50 Pigmentdispersion II-60 Bk dispersion including polymer II-51 Pigmentdispersion II-61 Bk dispersion including polymer II-52 Pigmentdispersion II-62 Bk dispersion including polymer II-53 Pigmentdispersion II-63 Bk dispersion including polymer II-54 Pigmentdispersion II-64 Bk dispersion including polymer II-55 Pigmentdispersion II-65 Bk dispersion including polymer II-56 Pigmentdispersion II-66 Bk dispersion including polymer II-57 Pigmentdispersion II-67 Bk dispersion including polymer II-58 Pigmentdispersion II-68 Bk dispersion including polymer II-59 Pigmentdispersion II-69 Bk dispersion including polymer II-60 Pigmentdispersion II-70 Bk dispersion including polymer II-61 Pigmentdispersion II-71 Bk dispersion including polymer II-62 Pigmentdispersion II-72 Bk dispersion including polymer II-63 Pigmentdispersion II-73 Bk dispersion including polymer II-64 Pigmentdispersion II-74 Bk dispersion including polymer II-65 Pigmentdispersion II-75 Bk dispersion including polymer II-66 Pigmentdispersion II-76 Bk dispersion including polymer II-67 Pigmentdispersion II-77 Bk dispersion including polymer II-68 Pigmentdispersion II-78 Bk dispersion including polymer II-69 Pigmentdispersion II-79 Bk dispersion including polymer II-70 Pigmentdispersion II-80 Bk dispersion including polymer II-71 Pigmentdispersion II-81 Bk dispersion including polymer II-72 Pigmentdispersion II-82 Bk dispersion including polymer II-73 Pigmentdispersion II-83 Bk dispersion including polymer II-74 Pigmentdispersion II-84 Bk dispersion including polymer II-75 Pigmentdispersion II-85 Bk dispersion including polymer II-76 Pigmentdispersion II-86 Bk dispersion including polymer II-77 Pigmentdispersion II-87 Low-molecular-weight bisphosphonic 40 acid *1 Aqueoussolution of polymer I-14 including a solid content of 10% by weightGlycerin 10 1,3-butanediol 20 2-ethyl-1,3- 1 hexanediol 2,2,4- 1trimethyl-1,3- pentadiol Surfactant 2 (Zonyl FS-300) Distilled water 26Total 100 *1: Low-molecular-weight bisphosphonic acid =1-hydroxyethylidene-1,1-bisphosphonic acid

The inks for inkjet recording of Examples II-1 to II-81 and ComparativeExamples II-1 to II-6 were evaluated by the following methods. Theresults are shown in Table II-7.

<Image Density (ID)>

In an environment of 23° C. and 50 RH, the ink was filled in an inkjetprinter IPSiO GX5000 from Ricoh Company, Ltd. After a chart on whichgeneral marks “▪” of JIS X 0208 (1997), 2223 having 64 points aredescribed by Microsoft Word 2003 was printed on a plain paper 1 (XEROX4200 from XEROX, Inc.) and a plain paper 2 (My Paper from Ricoh Company,Ltd.), the image density of “▪” was evaluated using X-Rite938 fromX-Rite, Inc. Then, the printing mode was “plain paper-fast” mode by adriver of the printer without color calibration.

Image density was evaluated under the following standard.

(Black)

A: not less than 1.25

B: not less than 1.20 and less than 1.25

C: not less than 1.10 and less than 1.20

D: less than 1.10

E: Unprintable as pigment was gelated and undispersible

(Yellow)

A: not less than 0.80

B: not less than 0.75 and less than 0.80

C: not less than 0.70 and less than 0.75

D: less than 0.70

E: Unprintable as pigment was gelated and undispersible

(Magenta)

A: not less than 0.95

B: not less than 0.85 and less than 0.95

C: not less than 0.75 and less than 0.85

D: less than 0.75

E: Unprintable as pigment was gelated and undispersible

(Cyan)

A: not less than 1.05

B: not less than 0.95 and less than 1.05

C: not less than 0.85 and less than 0.95

D: less than 0.85

E: Unprintable as pigment was gelated and undispersible

<Storage Stability of Pigment Dispersion>

Each of the pigment dispersions was placed in a polyethylene containerand sealed.

The viscosity after stored at 60° C. for 1 week was measured to evaluateunder the following standard, compared with the initial viscosity.

Viscosity Variation(%)=(Viscosity after Stored/Viscosity beforeStored)×100

The viscosity was measured by a viscometer RE500L from TOKI SANGYO CO.,LTD. at 25° C., adjusting the rotational number at from 50 to 100 rpmaccording the viscosity.

A: Viscosity variation was not greater than ±5%

B: Viscosity variation was greater than ±5% and not greater than ±8%

C: Viscosity variation was greater than ±8% and not greater than ±10%

D: Viscosity variation was greater than ±10% and not greater than ±30%

E: Viscosity variation was greater than ±30% (Unevaluable as pigment wasgelated)<

<Storage Stability of Ink>

Each of the inks was filled in an ink cartridge. The viscosity afterstored at 60° C. for 1 week was measured to evaluate under the followingstandard, compared with the initial viscosity.

Viscosity Variation(%)=(Viscosity after Stored/Viscosity beforeStored)×100

The viscosity was measured by a viscometer RE500L from TOKI SANGYO CO.,LTD. at 25° C., adjusting the rotational number at from 50 to 100 rpmaccording the viscosity.

A: Viscosity variation was not greater than ±5%

B: Viscosity variation was greater than ±5% and not greater than ±8%

C: Viscosity variation was greater than ±8% and not greater than ±10%

D: Viscosity variation was greater than ±10% and not greater than ±30%

E: Viscosity variation was greater than ±30% (Unevaluable as pigment wasgelated)

TABLE II-7 Evaluation Results Storage Stability Stor- ID ID of agePigment Plain Plain Pigment Stability Dispersion Paper 1 Paper 2Dispersion of Ink Example II-1 Pigment B B B C Dispersion II-1 ExampleII-2 Pigment B B A B Dispersion II-2 Example II-3 Pigment A A A ADispersion II-3 Example II-4 Pigment A A A A Dispersion II-4 ExampleII-5 Pigment A A A A Dispersion II-5 Example II-6 Pigment A A A ADispersion II-6 Example II-7 Pigment B B A A Dispersion II-7 ExampleII-8 Pigment A B A A Dispersion II-8 Example II-9 Pigment A A A ADispersion II-9 Example II-10 Pigment A A A A Dispersion II-10 ExampleII-11 Pigment A A A A Dispersion II-11 Example II-12 Pigment A A A ADispersion II-12 Example II-13 Pigment A A A A Dispersion II-13 ExampleII-14 Pigment A A A A Dispersion II-14 Example II-15 Pigment A A A BDispersion II-15 Example II-16 Pigment A A B B Dispersion II-16 ExampleII-17 Pigment A A A A Dispersion II-17 Example II-18 Pigment A A A ADispersion II-18 Example II-19 Pigment A A A A Dispersion II-19 ExampleII-20 Pigment A A A A Dispersion II-20 Example II-21 Pigment A A A ADispersion II-21 Example II-22 Pigment A A A A Dispersion II-22 ExampleII-23 Pigment A A A A Dispersion II-23 Example II-24 Pigment A A A ADispersion II-24 Example II-25 Pigment A A A A Dispersion II-25 ExampleII-26 Pigment A A A A Dispersion II-26 Example II-27 Pigment A A A ADispersion II-27 Example II-28 Pigment A A A A Dispersion II-28 ExampleII-29 Pigment A A A A Dispersion II-29 Example II-30 Pigment A A A ADispersion II-30 Example II-31 Pigment A A A C Dispersion II-31 ExampleII-32 Pigment A A A A Dispersion II-32 Example II-33 Pigment A A A BDispersion II-33 Example II-34 Pigment A A A A Dispersion II-34 ExampleII-35 Pigment A A A A Dispersion II-35 Example II-36 Pigment A A A ADispersion II-36 Example II-37 Pigment A A A A Dispersion II-37 ExampleII-38 Pigment A A A A Dispersion II-38 Example II-39 Pigment B B A ADispersion II-39 Example II-40 Pigment A B A A Dispersion II-40 ExampleII-41 Pigment A A A B Dispersion II-41 Example II-42 Pigment A A B BDispersion II-42 Example II-43 Pigment A A A A dispersion II-43 ExampleII-44 Pigment B B B C dispersion II-47 Example II-45 Pigment B B A Bdispersion II-48 Example II-46 Pigment A A A A dispersion II-49 ExampleII-47 Pigment A A A A dispersion II-50 Example II-48 Pigment A A A Adispersion II-51 Example II-49 Pigment A A A A dispersion II-52 ExampleII-50 Pigment B B A A dispersion II-53 Example II-51 Pigment A B A Adispersion II-54 Example II-52 Pigment A A A A dispersion II-55 ExampleII-53 Pigment A A A A dispersion II-56 Example II-54 Pigment A A A Adispersion II-57 Example II-55 Pigment A A A A dispersion II-58 ExampleII-56 Pigment A A A A dispersion II-59 Example II-57 Pigment A A A Adispersion II-60 Example II-58 Pigment A A A B dispersion II-61 ExampleII-59 Pigment A A B B dispersion II-62 Example II-60 Pigment A A A Adispersion II-63 Example II-61 Pigment A A A A dispersion II-64 ExampleII-62 Pigment A A A A dispersion II-65 Example II-63 Pigment A A A Adispersion II-66 Example II-64 Pigment A A A A dispersion II-67 ExampleII-65 Pigment A A A A dispersion II-68 Example II-66 Pigment A A A Adispersion II-69 Example II-67 Pigment A A A A dispersion II-70 ExampleII-68 Pigment A A A A dispersion II-71 Example II-69 Pigment A A A Adispersion II-72 Example II-70 Pigment A A A A dispersion II-73 ExampleII-71 Pigment A A A A dispersion II-74 Example II-72 Pigment A A A Adispersion II-75 Example II-73 Pigment A A A A dispersion II-76 ExampleII-74 Pigment A A A C dispersion II-77 Example II-75 Pigment A A A Adispersion II-78 Example II-76 Pigment A A A B dispersion II-79 ExampleII-77 Pigment B B A A dispersion II-80 Example II-78 Pigment A B A Adispersion II-81 Example II-79 Pigment A A A B dispersion II-82 ExampleII-80 Pigment A A B B dispersion II-83 Example II-81 Pigment A A A Adispersion II-84 Comparative Pigment C C E E Example II-1 DispersionII-44 Comparative Pigment E C E E Example II-2 Dispersion II-45Comparative Pigment E E E E Example II-3 Dispersion II-46 ComparativePigment C C E E Example II-4 dispersion II-85 Comparative Pigment E C EE Example II-5 dispersion II-86 Comparative Pigment E E E E Example II-6dispersion II-87

Table II-7 shows the inks of Examples produce images having higher imagedensity than those produced by the inks of Comparative Examples even ontypical plain papers, and have good storage stability even whenincluding the hydrosoluble organic solvent in an amount greater than 20%by weight.

Having now fully described the invention, it will be apparent to one ofordinary skill in the art that many changes and modifications can bemade thereto without departing from the spirit and scope of theinvention as set forth therein.

What is claimed is:
 1. An ink for inkjet recording, comprising: water; ahydrosoluble solvent, a pigment, and a copolymer comprising a salt of adiphosphonic acid group; wherein the copolymer comprising a salt of adiphosphonic acid group comprises structural units having the followingformulae (1) and (2):

wherein X represents an alkylene group having 1 to 3 carbon atoms, eachof R₁ and R₂ represents a hydrogen atom or a methyl group, M⁺ representsan alkali metal ion, an organic ammonium ion or a proton and Z₁represents a hydrocarbon group having 6 to 22 carbon atoms, wherein thealkali metal ion or the organic ammonium ion and the proton may bemixed, and half or more of the M⁺ are alkali metal ions or the organicammonium ions.
 2. The ink for inkjet recording of claim 1, wherein thecopolymer comprising a salt of a diphosphonic acid group furthercomprises a structural unit having the following formula (3a) or (3b):

wherein R₃ represents a hydrogen atom or a methyl group; each of R₁₀ andR₁₁ represents an alkyl group having 1 to 3 carbon atoms; Y representsan alkylene group having 1 to 4 carbon atoms; and Y₁ represents analkylene group having 1 to 3 carbon atoms.
 3. The ink for inkjetrecording of claim 1, wherein Z₁ represents a benzyl group, a phenetylgroup or an alkyl group having 12 to 22 carbon atoms.
 4. The ink forinkjet recording of claim 1, wherein the copolymer comprises thestructural unit having the following formula (1) in an amount of from 30to 70% by weight.
 5. The ink for inkjet recording of claim 1, whereinthe copolymer comprises the structural unit having the following formula(1) in an amount of from 40 to 60% by weight.
 6. The ink for inkjetrecording of claim 1, wherein an aqueous solution of the copolymerhaving a concentration of 10% by weight has a viscosity of from 1.5 to4.0 mPa·s at 25° C.
 7. The ink for inkjet recording of claim 1, whereinM⁺ is a tetraalkylammonium ion having 1 to 5 alkyl groups.
 8. An ink forinkjet recording, comprising: water; a hydrosoluble solvent, a pigment,and a copolymer comprising a salt of a diphosphonic acid group; whereinthe copolymer comprising a salt of a diphosphonic acid group issynthesized by radical polymerization with monomers having the followingformulae (4) and (5) as starting materials:

wherein X represents an alkylene group having 1 to 3 carbon atoms, eachof R₄ and R₅ represents a hydrogen atom or a methyl group, M⁺ representsan alkali metal ion, an organic ammonium ion or a proton and Z₂represents a hydrocarbon group having 6 to 22 carbon atoms.
 9. The inkfor inkjet recording of claim 8, wherein the copolymer comprising a saltof a diphosphonic acid group further comprises a structural unit havingthe following formula (6a) or (6b):

wherein R₆ represents a hydrogen atom or a methyl group; each of R₁₂ andR₁₃ represents an alkyl group having 1 to 3 carbon atoms; Y representsan alkylene group having 1 to 4 carbon atoms.
 10. The ink for inkjetrecording of claim 8, wherein M⁺ is a tetraalkylammonium ion having 1 to5 alkyl groups.
 11. An ink cartridge containing the ink for inkjetrecording according to claim 1 in a container.
 12. An inkjet recordingmethod, comprising: applying a stimulation to the ink for inkjetrecording according to claim 1 to fly and record an image.
 13. An inkjetrecorder, comprising: a flyer configured to apply a stimulation to theink for inkjet recording according to claim 1 to fly and record animage.
 14. An ink-recorded matter having an image recorded by the inkfor inkjet recording according to claim
 1. 15. An ink cartridgecontaining the ink for inkjet recording according to claim 8 in acontainer.
 16. An inkjet recording method, comprising: applying astimulation to the ink for inkjet recording according to claim 8 to flyand record an image.
 17. An inkjet recorder, comprising: a flyerconfigured to apply a stimulation to the ink for inkjet recordingaccording to claim 8 to fly and record an image.
 18. An ink-recordedmatter having an image recorded by the ink for inkjet recordingaccording to claim 8.